Process and a composition for immunizing plants against diseases

ABSTRACT

A method and composition for the immunization of healthy useful plants against plant diseases containing as active ingredients compounds of formula ##STR1## in which: X is hydrogen, halogen, hydroxy, methyl, methoxy, HOOC or MOOC; 
     Y is hydrogen, halogen, SO 3  H, SO 3  M, nitro, hydroxy or amino, M being the molar equivalent of an alkali metal or alkaline earth metal ion that is formed from a corresponding base or basic compound; and 
     Z is cyano or --CO--A; 
     A represents either --OH or --SH, the hydrogen atom of which may also be replaced by the molar equivalent of an inorganic or organic cationic residue, 
     or wherein A represents any other organic residue which has a molecular weight of less than 900 and which may also contain one, or more than one, hetero atom, including the salts of the phytophysiologically tolerable 7-carboxylic acid or 7-thiocarboxylic acid with primary, secondary or tertiary amines or with inorganic bases.

This application is a continuation of application Ser. No. 494,190,filed Mar. 15, 1990, now abandoned, which in turn is a divisional ofapplication Ser. No. 234,241, filed Aug. 18, 1988now U.S. Pat. No.4,931,581.

The present invention relates to a method and composition forartificially producing in plants defence mechanisms against attack bydiseases, and to measures and substances for carrying out this method.

Plants are exposed to a great variety of microbial influences bybacteria, viruses and fungi that parasiticise on the plant.

Previous efforts in the field of plant protection have as a rule beenlimited to strengthening the plant generally, for example by cultivationand fertilisation, and to preventing or controlling a threatened orexisting disease attack by the application of safeners having a directaction (=microbicides).

The problem underlying the present invention is to activate in a gentlemanner the defence mechanisms latent in a plant, so that the plantitself is able to recognise and combat an attack by a pathogen. Thisprocess may be termed immunisation.

According to the present invention the solution to the problem ofcontrolling disease in plants lies in the artificial chemical activationof the plant's own defence mechanisms against pathogenic microbiologicalinfluences. Even a single chemical application can produce in the planta prolonged resistance to certain pathogens lasting from several weeksto several months. The fundamental difference with respect toconventional methods of controlling disease therefore lies in the use ofsubstances which have no microbicidal action of their own, but stimulatethe plant's capacity to defend itself against microbial infections andwhich, as a result of their low application rates, do not harm the plantitself or the locus thereof.

The invention relates to a method for immunising plants against attackby disease, characterised by the application to the plant to beprotected, to parts of the plant or to the locus thereof, of smallamounts of a 7-cyano-1,2,3-benzothiadiazole derivative or a derivativeof 1,2,3-benzothiadiazole-7-carboxylic acid of the formula I below.##STR2## In this formula: X is hydrogen, halogen, hydroxy, methyl,methoxy, HOOC or MOOC;

Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro, hydroxy or amino, M beingthe molar equivalent of an alkali metal or alkaline earth metal ion thatis formed from a corresponding base or basic compound; and

Z is cyano or --CO--A;

wherein A represents either --OH or --SH, the hydrogen atom of which mayalso be replaced by the molar equivalent of an inorganic or organiccationic residue,

or wherein A represents any other organic residue which has a molecularweight of less than 900 and which may also contain one, or more thanone, hetero atom.

The X and Y containing 1,2,3-benzothiadizole-7-carboxylic acid of theformula I and its salts essentially constitutes the main activeprinciple that triggers in the plant the defence mechanism againstpathogens. Also included are the 7-cyano compounds covered by formula Iwhich may undergo conversion in the plant metabolism to the 7-carboxylicacid and vice versa. It will be readily understood that the contributionto biological activity that is imparted by substituent A will be oflesser importance. Hence it may also be understood that, despite thewidely differing structural variations of the substituent A,substantially equivalent biological responses will be induced with thecompounds of formula I. However, a substituent A should not hinder theactive principle of the 7-substituted 1,2,3-benzothiadiazole toostrongly.

Preferred substituents A are therefore cationic or any other organicresidues having a molecular weight of less than 600, while those of lessthan 400 are especially preferred.

Among the 7-cyano compounds, those are preferred, wherein X representshydrogen, halogen or methyl and Y represents hydrogen or halogen.

An important object of this invention is to provide the followingcompounds of formula I, corresponding plant protection compositions andprocesses for their application: ##STR3##

In this formula:

X is hydrogen, halogen, hydroxy, methyl, methoxy, HOOC or MOOC;

Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro, hydroxy or amino, M beingthe molar equivalent of an alkali metal or alkaline earth metal ion thatis formed from a corresponding base or basic compound; and

Z is cyano or --CO--A;

A is UR, N(R₁)R₂ or U¹ N(═C)_(n) (R₃)R₄ ;

M is the molar equivalent of an alkali metal or alkaline earth metal ionthat has been formed from a corresponding base or basic compound;

U is oxygen or sulfur;

U¹ is oxygen or --N(R₅)--;

R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl that is substituted byhalogen, cyano, nitro, hydroxy, U-C₁ -C₃ alkyl or by C₂ -C₄ dialkylaminoor is interrupted by the CO group, (T)-COOH or (T)-COOC₁ -C₄ alkyl, C₃-C₆ alkenyl, halo-substituted C₃ -C₆ alkenyl, C₃ -C₆ alkynyl,halo-substituted C₃ -C₆ alkynyl, (T)_(n) -C₃ -C₈ cycloalkyl, or a groupselected from the following: ##STR4## each of X^(a), X^(b) and X^(c),independently of the others, is hydrogen, halogen, hydroxy, cyano, HOOC,MOOC, C₁ -C₃ alkyl-OOC, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkylhaving up to 5 halogen atoms, especially fluorine atoms; or X^(a) is C₁-C₂ haloalkoxy having up to 5 halogen atoms, nitro, dimethylamino,phenyl, phenoxy, benzyloxy, sulfamoyl and X^(b) and X^(c) are bothhydrogen; or

X^(a) is phenyl, phenoxy or benzyloxy and

X^(b) is halogen or methyl and X^(c) is hydrogen; or

X^(a), X^(b) and X^(c) together are 4 or 5 fluorine atoms; naphth is anaphthyl radical that is unsubstituted or is substituted by halogen,methyl, methoxy or by nitro;

W is a 5- to 7-membered saturated or unsaturated heterocycle having from1 to 3 hetero atoms from the group O, N and S that is unsubstituted oris substituted by halogen, trifluoromethyl, cyano, C₁ -C₂ alkyl or by aC₁ -C₂ -alkoxycarbonyl-C₂ -C₄ alkyleneamino(imino) radical, or is amonosaccharide radical;

T is a bridge member --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)--, --CCH₃(CH₃)--, --CH₂ CH₂ CH₂ -- or --CH₂ CH₂ O--;

R₁ is hydrogen, C₁ -C₅ alkyl, C₁ -C₅ alkyl interrupted by an oxygen orsulfur atom, C₁ -C₅ alkyl substituted by halogen, cyano, HOOC or by C₁-C₂ alkyl-OOC, C₁ -C₅ alkyl interrupted by an oxygen or sulfur atom andsubstituted by halogen, cyano, HOOC or by C₁ -C₂ alkyl-OOC, C₃ -C₅alkenyl, C₃ -C₅ -alkenyl substituted by C₁ -C₃ alkyl-OOC, C₃ -C₅-alkynyl C₃ -C₅ -alkynyl substituted by C₁ -C₃ alkyl-OOC, (T)_(n) -C₃-C₆ cycloalkyl, (T)_(n) -C₃ -C₆ cycloalkyl substituted by C₁ -C₃alkyl-OOC, (T)_(n) -phenyl, or (T)_(n) -phenyl substituted in the phenylmoiety by halogen, hydroxy, methyl, methoxy, CF₃, cyano, HOOC or byMOOC; R₂ is hydrogen, hydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkyl substituted bycyano or by C₁ -C₃ alkoxy, C₁ -C₄ alkoxy, a 3- to 6-membered saturatedor unsaturated heterocycle containing O, N or S as hetero atoms;

R₁ and R₂ together are a heterocycle W;

R₃ is hydrogen, cyano, C₁ -C₆ alkyl, phenyl, phenyl substituted byhalogen, hydroxy, methyl, methoxy, HOOC or by MOOC, or a heterocycle W;

R₄ is hydrogen, C₁ -C₆ alkyl, CONH2, CONH--CONH-C₁ -C₃ alkyl, C₁ -C₃alkanoyl, C₁ -C₃ alkanoyl substituted by halogen or by C₁ -C₃ alkoxy, C₃-C₅ alkenoyl, or C₃ -C₅ alkenoyl substituted by halogen or by C₁ -C₃alkoxy;

R₃ and R₄ together are a heterocycle W or a carbocyclic ring W';

W' is a carbocyclic radical having from 3 to 7 ring carbon atoms;

R₅ is hydrogen or methyl;

R₆ is hydrogen or C₁ -C₄ alkyl; and

n is 0 or 1;

and in compounds of formula I the organic radical A has a molecularweight of less than 900; and in the case where U is oxygen or sulfur,the salts of the phytophysiologically tolerable 7-carboxylic acid withprimary, secondary or tertiary amines or with inorganic bases areincluded.

A special group of active ingredients for the method according to theinvention comprises the following compounds of formula I, wherein:

X is hydrogen, halogen, hydroxy, methyl, methoxy, HOOC or MOOC;

Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro, hydroxy or amino;

Z is cyano or COA;

A is UR, N(R₁)R₂ or U1N(═C)n(R₃)R₄ ;

M is the molar equivalent of an alkali metal or alkaline earth metal ionthat has been formed from a corresponding base or basic compound;

U is oxygen or sulfur;

U¹ is oxygen or --N(R₅)--;

R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl substituted by halogen, cyano,nitro, hydroxy, alkoxy or by U-C₁ -C₃ alkyl, (T)-COOH or (T)-COOC₁ -C₄alkyl, C₂ -C₆ alkenyl, halo-substituted C₃ -C₆ alkenyl, C₃ -C₆ alkynyl,halo-substituted C₃ -C₆ alkynyl, (T)_(n) -C₃ -C₈ cycloalkyl, or a groupselected from the following: ##STR5## W is a 5- to 7-membered saturatedor unsaturated heterocycle having from 1 to 3 hetero atoms from thegroup O, N and S that is unsubstituted or is substituted by halogen,trifluoromethyl, cyano, C₁ -C₂ alkyl or by a C₁ -C₂ -alkoxycarbonyl-C₂-C₄ alkyleneimino radical, or is a monosaccharide radical;

T is a bridge member --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)-- or --CCH₃(CH₃)--,

R₁ is hydrogen, C₁ -C₅ alkyl, C₁ -C₅ alkyl interrupted by an oxygen orsulfur atom, C₁ -C₅ alkyl substituted by halogen, cyano, HOOC or by C₁-C₂ alkyl-OOC, C₁ -C₅ alkyl interrupted by an oxygen or sulfur atom andsubstituted by halogen, cyano, HOOC or by C₁ -C₂ alkyl-OOC, C₃ -C₅alkenyl, C₃ -C₅ -alkenyl substituted by C₁ -C₃ alkyl-OOC, C₃ -C₅alkynyl, C₃ -C₅ -alkynyl substituted by C₁ -C₃ alkyl-OOC, (T)_(n) -C₃-C₆ cycloalkyl, (T)_(n) -C₃ -C₆ cycloalkyl substituted by C₁ -C₃alkyl-OOC, (T)_(n) -phenyl or (T)_(n) -phenyl substituted in the phenylmoiety by halogen, hydroxy, methyl, methoxy, CF₃, cyano, HOOC or byMOOC;

R₂ is hydrogen, hydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkyl substituted by cyanoor by C₁ -C₃ alkoxy, C₁ -C₄ alkoxy, or a 3- to 6-membered saturated orunsaturated heterocycle having O, N or S as hetero atoms;

R₁ and R₂ together are a heterocycle W;

R₃ is hydrogen, cyano, C₁ -C₆ alkyl, phenyl, phenyl substituted byhalogen, hydroxy, methyl, methoxy, HOOC or by MOOC, or a heterocycle W;

R₄ is hydrogen, C₁ -C₆ alkyl, CONH₂, CONH--CONH-C₁ -C₃ alkyl, C₁ -C₃alkanoyl, C₁ -C₃ alkanoyl substituted by halogen or by C₁ -C₃ alkoxy, C₃-C₅ alkenoyl, or C₃ -C₅ alkenoyl substituted by halogen or by C₁ -C₃alkoxy;

R₃ and R₄ together are a heterocycle W or a carbocyclic ring W';

W' is a carbocyclic radical having from 3 to 7 ring carbon atoms;

R₅ is hydrogen or methyl;

R₆ is hydrogen or C₁ -C₄ alkyl; and

n is 0 or 1;

and the phytophysiologically tolerable salts of the 7-carboxylic acidsand 7-thiocarboxylic acids with primary, secondary and tertiary aminesare included.

The present invention relates also to compositions for use against plantdiseases that contain compounds of formula I as active ingredients. Theinvention relates also to the preparation of the said compositions andto the preparation of those active ingredients which are novel. Theinvention relates also to the use of the active ingredients or thecompositions for protecting plants against attack by phytopathogenicmicroorganisms, for example fungi, bacteria and viruses.

As mentioned above, compounds of formula I are not microbicides in theconventional sense of having a direct action against the pathogens but,as can be shown hereinbelow, are in principle ineffective against suchpathogens in the absence of a plant (=in vitro). When such a directmicrobicidal action does nevertheless occasionally occur, it isgenerally an additional action brought about by certain structuralelements in the molecule which superimpose such a secondary action on,but do not replace, the existing immunising effect.

The principle causing immunising action is based essentially on thespecific basic 1,2,3-benzothiadiazole structure of formula I substitutedin the 7-position by an acid function, whilst the ability of the1,2,3-benzothiadiazole derivatives to penetrate the plants or theirmetabolism is dependent upon the radicals defined under A and the saltsof the 7-acid (vehicle function).

Compounds of formula I that are therefore preferred as regards theirimmunising potential are those in which the organic radical A has amolecular weight of less than 600 and more especially a molecular weightof less than 400. Compounds having Z=CN are also preferred.

In a special variant, compounds of formula I preferred for plantimmunisation are those in which the substituent Z is cyano oralternatively a radical A the molecular weight of which constitutes from5.0% to 85%, preferably from 7.8% to 60%, of the molecular weight of thewhole molecule of formula I.

The application rate for such immunisation agents of formula I is lessthan 1 kg of active ingredient/hectare, preferably less than 500 g ofactive ingredient/hectare, and more especially from 50 to 300 g ofactive ingredient/hectare.

The term "hetero atoms" also includes elements other than N, O and S,for example Si or P.

Suitable cationic radicals for an M-OOC group are metals and organicbases. Alkali metals and alkaline earth metals are advantageous asmetals, but any others may also come into consideration. Suitableorganic bases are amines, especially having aliphatic, aromatic,araliphatic and/or cycloaliphatic radicals.

Halogen on its own or as a constituent of another substituent isfluorine, chlorine, bromine or iodine, preferably fluorine, chlorine orbromine. Alkyl on its own or as a constituent of another substituent isto be understood as meaning straight-chain or branched alkyl groups.Depending upon the number of carbon atoms indicated, they are, forexample, the following groups: methyl, ethyl and the isomers of propyl,butyl, pentyl, hexyl, heptyl or octyl, such as, for example, isopropyl,isobutyl, tert.-butyl, sec.-butyl or isopentyl. Cycloalkyl is, forexample, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkenyl is, for example, propen-1-yl, allyl, buten-1-yl, buten-2-yl orbuten-3-yl, and chains having several double bonds. Alkynyl is, forexample, propyn-2-yl, butyn-1-yl, butyn-2-yl, pentyn-4-yl, etc.,preferably propargyl.

Suitable bases or compounds having basic character are inorganic basesor base formers, such as, for example, hydroxides, carbonates andhydrogen carbonates of alkali metals and alkaline earth metals,preferably LiOH, NaOH, KOH, Mg(OH)₂ or Ca(OH)₂ ; and also NaHCO₃, KHCO₃,Na₂ CO₃ and K₂ CO₃.

Heterocycles are to be understood as being, for example: furan,tetrahydrofuran, thiophene, tetrahydropyran, pyrrole, pyrrolidine,imidazole, 1,2,4-triazole, piperidine, pyridine, pyrimidine, morpholineor azacycloheptane. They are especially: furan-2-yl,tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydropyran-2-yl,1,3-dioxolan-5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrolidin-1-yl,isoxazol-3-yl, isoxazol-4-yl, 1,2-dithiazolin-5-yl, imidazol-1-yl,1,2,4-triazol-1-yl, 1,3,4-triazol-1-yl, thiophen-2-yl, piperidin-1-yl,piperidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl,pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, morpholin-1-yl,azacycloheptan-1-yl or benzo-1,2,3-thiadiazol-7'-yl.

Salt-forming amines are to be regarded, for example, as the following:trimethylamine, triethylamine, tripropylamine, tributylamine,tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine,N,N-dimethylaniline, N,N-dimethyltoluidine,N,N-dimethyl-p-aminopyridine, N-methylpyrrolidine, N-methylpiperidine,N-methylpyrrolidine, N-methylimidazole, N-methylpyrrole,N-methylmorpholine, N-methylhexamethyleneimine, pyridine, quinoline,α-picoline, β-picoline, isoquinoline, pyrimidine, acridine,N,N,N',N'-tetramethylethylenediamine,N,N,N',N'-tetraethylethylenediamine, quinoxaline,N-propyldiisopropylamine, N,N-dimethylcyclohexylamine, 2,6-lutidine,2,4-lutidine, triethylenediamine and heterocyclic amines of themorpholine type.

A monosaccharide radical is to be understood as being, for example,glucofuranosyl, galactopyranosyl, allofuranosyl or mannityl, the OHgroups being free or acetylated or etherified by methyl, benzyl or byisopropylidenyl. Of the radicals mentioned, the diisopropylidenylderivatives are preferred, whilst of these in turn the followingradicals are especially preferred: diacetone-D-glucosidyl,1,2,3,4-di-O-isopropylidene-D-galactopyranos-6-yl,1,2,5,6-di-O-isopropylidene-D-mannit-3-yl,1,2,5,6-di-O-isopropylidene-4-D-allofuranos-3-yl, D-glucofuranos-3-yl,D-galacto-pyranos-6-yl, D-mannit-3-yl, D-allofuranos-4-yl,mannopyranos-1-yl, 2-methyl-D-glucosid-6-yl,1,2,5,6-tetraacetyl-D-galactopyranos-3-yl and2,3,5-tribenzylribofuranos-1-yl.

As a result of their pronounced protective properties against attack byphytopathogenic microorganisms, preferred active ingredients are thoseof which the structures carry the following substituents or combinationsof these substituents with one another:

X and Y are hydrogen;

Z is cyano or COA;

A is UR or U¹ N(═C)_(n) (R₃)R₄ ;

U is oxygen;

U¹ is oxygen or --N(R₅)--;

R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl substituted by halogen or byC₁ -C₃ -alkoxy, C₃ -C₆ alkenyl, halo-substituted C₃ -C₆ alkenyl, C₃ -C₆alkynyl, halo-substitued C₃ -C₆ alkynyl, (T)_(n) -C_(3-C) ₈ cycloalkyl,benzyl, halogenated benzyl, methoxybenzyl, (T)_(n) -Si(CH₃)₃,(T)-P(O)(C₁ -C₄ alkyl)CH₃, (T)-P(O)(OC₁ -C₄ alkyl)₂ or the group (T)_(n)-W;

W is a 5- to 7-membered saturated or unsaturated unsubstitutedheterocycle having from 1 to 3 hetero atoms from the group O, N and S,or is diacetone-D-glucosidyl;

T is a bridge member --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)--, --CCH₃ (CH₃)--or --CH₂ CH₂ CH₂ --;

R₃ is hydrogen, cyano, C₁ -C₆ alkyl, phenyl or W;

R₄ is hydrogen, C₁ -C₆ alkyl, CONH₂, CONH--CONH-C₁ -C₃ alkyl, C₁ -C₃alkanoyl or C₃ -C₅ alkenoyl;

R₃ and R₄ together are W or W';

W is a 5- to 7-membered saturated or unsaturated heterocycle having from1 to 3 hetero atoms from the group O, N and S;

W' is a radical from the group: ##STR6## n is 0 or 1.

A special group of active ingredients having preferred microbicidalaction against phytopathogenic microorganisms comprises compounds havingthe following substituents or combinations of these substituents withone another:

X and Y are hydrogen;

Z is cyano or COA;

A is UR or U¹ N(═C)_(n) (R₃)R₄ ;

U is oxygen;

U¹ is oxygen or --N(R₅)--;

R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl substituted by halogen or byC₁ -C₃ alkoxy, C₃ -C₆ alkenyl, halo-substituted C₃ -C₆ alkenyl, C₃ -C₆alkynyl, halo-substituted C₃ -C₆ alkynyl, (T)_(n) -C₃ -C₈ cycloalkyl,benzyl, halogenated benzyl, (T)_(n) -Si(CH₃)₃, (T)-P(O)(C₁ -C₄alkyl)CH₃, (T)-P(O)(OC₁ -C₄ alkyl)₂ or the group (T)_(n) -W;

W is a 5- to 7-membered saturated or unsaturated unsubstitutedheterocycle having from 1 to 3 hetero atoms from the group O, N and S,or is diacetone-D-glucosidyl;

T is a bridge member --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)-- or --CCH₃(CH₃)--;

R₃ is hydrogen, cyano, C₁ -C₆ alkyl, phenyl or W;

R₄ is hydrogen, C₁ -C₆ alkyl, CONH₂, CONH--CONH-C₁ -C₃ alkyl, C₁ -C₃alkanoyl or C₃ -C₅ alkenoyl;

R₃ and R₄ together are W or W';

W is a 5- to 7-membered saturated or unsaturated heterocycle having from1 to 3 hetero atoms from the group O, N and S;

W' is a radical from the group: ##STR7## n is 0 or 1.

Most of the compounds falling within the scope of formula I are novel;the others are known. For example, German Offenlegungsschrift No. 1 695786 and French Patent Specification No. 1 541 415 disclose somecompounds in general form as biocidal active ingredients for use inherbicidal, insecticidal and fungicidal compositions. However, none ofthese known individual compounds falling within the scope of formula Iof the present invention is specifically described as having fungicidalactivity. Furthermore, benzo-1,2,3-thiadiazole-7-carboxylic acid isknown from J. Chem. Soc. (C) 1971, 3997, but no details of biologicalproperties are given.

The novel compounds of the present invention are defined in thefollowing groups:

Compounds of formula I' ##STR8## in which: X is hydrogen, halogen,hydroxy, methyl, methoxy, HOOC or MOOC;

Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro, hydroxy or amino;

Z is cyano or COA;

A is UR, N(R₁)R₂ or U¹ N(═C)_(n) (R₃)R₄ ;

M is the molar equivalent of an alkali metal or alkaline earth metal ionthat has been formed from a corresponding base or basic compound;

U is oxygen or sulfur;

U¹ is oxygen or --N(R₅)--;

R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl substituted by halogen, cyano,nitro, hydroxy or by U-C₁ -C₃ alkyl,

(T)-COOH or (T)-COOC₁ -C₄ alkyl, C₃ -C₆ alkenyl, halo-substituted C₃ -C₆alkenyl, C₃ -C₆ alkynyl, halo-substituted C₃ -C₆ alkynyl, (T)_(n) -C₃-C₈ cycloalkyl, or a group selected from the following: ##STR9## each ofX^(a), X^(b) and X^(c), independently of the others, is hydrogen,halogen, hydroxy, cyano, HOOC, MOOC, C₁ -C₃ alkyl-OCC, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₂ haloalkyl having up to 5 halogen atoms, especiallyfluorine atoms; or X^(a) is C₁ -C₂ haloalkoxy having up to 5 halogenatoms, nitro, dimethylamino, phenyl, phenoxy, benzyloxy or sulfamoyloxyand X^(b) and X^(c) are both hydrogen; or

X^(a) is phenyl, phenoxy or benzyloxy and X^(b) is halogen or methyl andX^(c) is hydrogen; or

X^(a), X^(b) and X^(c) together are 4 or 5 fluorine atoms;

naphth is a naphthyl radical that is unsubstituted or is substituted byhalogen, methyl, methoxy or by nitro;

W is a 5- to 7-membered saturated or unsaturated heterocycle having from1 to 3 hetero atoms from the group O, N and S that is unsubstituted oris substituted by halogen, trifluoromethyl, cyano, C₁ -C₂ alkyl or by aC₁ -C₂ alkoxycarbonyl-C₂ -C₄ alkyleneimino radical, or is amonosaccharide radical;

T is a bridge member --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)--, --CH₂ CH₂ CH₂-- or --CH₂ CH₂ O--;

R₁ is hydrogen, C₁ -C₅ alkyl, C₁ -C₅ alkyl interrupted by an oxygen orsulfur atom, C₁ -C₅ alkyl substituted by halogen, cyano, HOOC or by C₁-C₂ alkyl-OCC, C₁ -C₅ alkyl interrupted by an oxygen or sulfur atom andsubstituted by halogen, cyano, HOOC or by C₁ -C₂ alkyl-OOC, C₃ -C₅alkenyl, C₃ -C₅ alkenyl substituted by C₁ -C₃ alkyl-OOC, C₃ -C₅ alkynyl,C₃ -C₅ -alkynyl substituted by C₁ -C₃ alkyl-OOC, (T)_(n) -C₃ -C₆cycloalkyl, (T)_(n) -C₃ -C₆ cycloalkyl substituted by C₁ -C₃ alkyl-OOC,(T)_(n) -phenyl or (T)_(n) -phenyl substituted in the phenyl moiety byhalogen, hydroxy, methyl, CF₃, cyano, methoxy, HOOC or by MOOC;

R₂ is hydrogen, hydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkyl substituted by cyanoor by C₁ -C₃ alkoxy, C_(1-C) ₄ alkoxy, or a 3- to 6-membered saturatedor unsaturated heterocycle having O, N or S as hetero atoms;

R₁ and R₂ together are a heterocycle W;

R₃ is hydrogen, cyano, C₁ -C₆ alkyl, phenyl, phenyl substituted byhalogen, hydroxy, methyl, methoxy, HOOC or by MOOC, or a heterocycle W;

R₄ is hydrogen, C₁ -C₆ alkyl, CONH₂, CONH--CONH-C₁ -C₃ alkyl, C₁ -C₆alkanoyl, C₁ -C₃ alkanoyl substituted by halogen or by C₁ -C₃ alkoxy, C₃-C₅ alkenoyl, or C₃ -C₅ alkenoyl substituted by halogen or by C₁ -C₃alkoxy;

R₃ and R₄ together are a heterocycle W or a carbocyclic ring W';

W' is a carbocyclic radical having from 3 to 7 ring carbon atoms;

R₅ is hydrogen or methyl;

R₆ is hydrogen or C₁ -C₄ alkyl; and

n is 0 or 1;

1) with the exception of the compounds:

7-cyanobenzo-1,2,3-thiadiazole;

4-chloro-7-cyanobenzo-1,2,3-thiadiazole;

4,6-dibromo-7-cyanobenzo-1,2,3-thiadiazole;

benzo-1,2,3-thiadiazole-7-carboxylic acid;

benzo-1,2,3-thiadiazole-7-carboxylic acid methyl ester; or

2) with the proviso that if

Z is cyano, HOOC or methoxycarbonyl, each of X and Y, independently ofthe other, is not hydrogen, chlorine or bromine; or

3) with the proviso that if

Z is cyano, methoxycarbonyl, ethoxycarbonyl or HOOC, X is not hydrogen,halogen, hydroxy, methyl or methoxy and Y is not hydrogen, halogen,nitro or amino; or

4) with the proviso that if

Z is cyano, C₁ -C₄ alkoxycarbonyl or HOOC, X is not hydrogen, halogen,hydroxy, methyl or methoxy and Y is not hydrogen, halogen, nitro oramino.

A special group of novel active ingredients comprises the followingcompounds of formula I' in which:

X is hydrogen, halogen, hydroxy, methyl, methoxy, HOOC or MOOC;

Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro, hydroxy or amino;

Z is cyano or COA;

A is UR, N(R₁)R₂ or U¹ N(═C)_(n) (R₃)R₄ ;

M is the molar equivalent of an alkali metal or alkaline earth metal ionthat has been formed from a corresponding base or basic compound;

U is oxygen or sulfur;

U¹ is oxygen or --N(R₅)--;

R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl that is substituted byhalogen, cyano, nitro, hydroxy, alkoxy or by U-C₁ -C₃ alkyl, (T)-COOH or(T)-COOC₁ -C₄ alkyl, C₂ -C₆ alkenyl, halo-substituted C₃ -C₆ alkenyl, C₃-C₆ alkynyl, halo-substituted C₃ -C₆ alkynyl, (T)_(n) -C₃ -C₈cycloalkyl, or a group selected from the following: ##STR10## W is a 5-to 7-membered saturated or unsaturated heterocycle having from 1 to 3hetero atoms from the group O, N and S that is unsubstituted or issubstituted by halogen, trifluoromethyl, cyano, C₁ -C₂ alkyl or by a C₁-C₂ alkoxycarbonyl-C₂ -C₄ alkyleneimino radical, or is a monosaccharideradical;

T is a bridge member --CH₂ --, --CH₂ CH₂ -- or --CH(CH₃)--;

R₁ is hydrogen, C₁ -C₅ alkyl, C₁ -C₅ alkyl interrupted by an oxygen orsulfur atom, C₁ -C₅ alkyl substituted by halogen, cyano, HOOC or by C₁-C₂ alkyl-OOC, C₁ -C₅ alkyl interrupted by an oxygen or sulfur atom andsubstituted by halogen, cyano, HOOC or by C₁ -C₂ alkyl-OOC, C₃ -C₅alkenyl, C₃ -C₅ -alkenyl substituted by C₁ -C₃ alkyl-OOC, C₃ -C₅alkynyl, C₃ -C₅ -alkynyl substituted by C₁ -C₃ alkyl-OOC, (T)_(n) -C₃-C₆ cycloalkyl, (T)_(n) -C₃ -C₆ cycloalkyl substituted by C₁ -C₃alkyl-OOC, (T)_(n) -phenyl or (T)_(n) -phenyl substituted in the phenylmoiety by halogen, hydroxy, methyl, CF₃, cyano, methoxy, HOOC or byMOOC;

R₂ is hydrogen, hydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkyl substituted by cyanoor by C₁ -C₃ alkoxy, C₁ -C₄ alkoxy, or a 3- to 6-membered saturated orunsaturated heterocycle containing O, N or S as hetero atoms;

R₁ and R₂ together are a heterocycle W;

R₃ is hydrogen, cyano, C₁ -C₆ alkyl, phenyl, phenyl substituted byhalogen, hydroxy, methyl, methoxy, HOOC or by MOOC, or a heterocycle W;

R₄ is hydrogen, C₁ -C₆ alkyl, CONH₂, CONH--CONH-C₁ -C₃ alkyl, C₁ -C₃alkanoyl, C₁ -C₃ alkanoyl substituted by halogen or by C₁ -C₃ alkoxy, C₃-C₅ alkenoyl, or C₃ -C₅ alkenoyl substituted by halogen or by C₁ -C₃alkoxy;

R₃ and R₄ together are a heterocycle W or a carbocyclic ring W';

W' is a carbocyclic radical having from 3 to 7 ring carbon atoms;

R₅ is hydrogen or methyl;

R₆ is hydrogen or C₁ -C₄ alkyl; and

n is 0 or 1;

with the exception of the compounds:

7-cyanobenzo-1,2,3-thiadiazole;

4-chloro-7-cyanobenzo-1,2,3-thiadiazole;

4,6-dibromo-7-cyanobenzo-1,2,3-thiadiazole;

benzo-1,2,3-thiadiazole-7-carboxylic acid;

benzo-1,2,3-thiadiazole-7-carboxylic acid methyl ester.

The following compounds are preferred as active ingredients because oftheir excellent biological activity:

Group A (known compounds)

7-carboxylic acid-benzo-1,2,3-thiadiazole (Compound 1.1);

7-methoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.2).

Group B 1 (novel compounds)

7-ethoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.3);

7-n-propoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.4);

7-isopropoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.5);

7-n-butoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.6);

7-sec.-butoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.7);

7-tert.-butoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.8);

7-cyclopropylmethoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.28);

7-(2'-phenethoxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.33);

7-benzyloxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.34);

7-allyloxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.44);

7-propyn-2-yloxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.46);

N-ethylaminocarbonyl-2-cyano-2-oximinocarbonylbenzo-1,2,3-thiadiazole-7-ylacetamide(Compound 1.78);

sodium salt of benzo-1,2,3-thiadiazole-7-carboxylic acid (Compound1.112);

potassium salt of benzo-1,2,3-thiadiazole-7-carboxylic acid (Compound1.113);

triethylammonium salt of benzo-1,2,3-thiadiazole-7-carboxylic acid(Compound 1.114);

7-(1-phenethoxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.119);

7-(1-naphthylmethoxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.116);

7-(methylthiocarbonyl)-benzo-1,2,3-thiadiazole (Compound 2.1);

7-(ethylthiocarbonyl)-benzo-1,2,3-thiadiazole (Compound 2.2);

7-(benzylthiocarbonyl)-benzo-1,2,3-thiadiazole (Compound 2.5);

7-[(dicyanomethyl)-aminocarbonyl]-benzo-1,2,3-thiadiazole (Compound3.13);

1-amino-N-[(1,3,4-thiadiazole-2-yl)-(N-benzo-1,2,3-thiadiazoyl)]-2-methoxycarbonyl-1-propene(Compound 3.28);

1-amino-N-[(1,3,4-thiadiazol-2-yl)-(N-benzo-1,2,3-thiadiazoyl)]-2-methoxycarbonyl-1-butene(Compound 3.29);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(α-methylpropylidene)-hydrazine(Compound 4.2);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclobutylidene)-hydrazine(Compound 4.8);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclopentylidene)-hydrazine(Compound 4.9);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclohexylidene)-hydrazine(Compound 4.10);

2-(benzo-1,2,3-thiadiazole-7-carbonyl)-1-(2'-sec.-butyl)-hydrazine(Compound 5.2);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclopentyl)-hydrazine(Compound 5.7);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclohexyl)-hydrazine(Compound 5.8);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cycloheptyl)-hydrazine(Compound 5.9);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-1,2-diacetylhydrazine (Compound6.7);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-phenylhydrazine (Compound 6.8);

1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-pyridin-2'-ylhydrazine(Compound 6.9).

Group B 2 (novel compounds)

7-n-pentoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.9);

7-(4-methoxybenzyloxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.39);

7-(cycloheximino-oxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.72);

7-(3-hydroxy-n-propoxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.79);

1,2,5,6-di-O-isopropylidene-3-(7-benzo-1,2,3-thiadiazoyl)-D-glucofuranose(Compound 1.86);

7-furfuryloxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.96);

7-(1,2,4-triazol-1-yl)-methoxycarbonylbenzo-1,2,3-thiadiazole (Compound1.100);

7-(2-pyridylmethoxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.101);

7-trimethylsilylmethoxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.103);

7-[2-(trimethylsilyl)-ethoxycarbonyl]-benzo-1,2,3-thiadiazole (Compound1.104);

7-dimethylphosphono-ethoxycarbonylbenzo-1,2,3-thiadiazole (Compound1.108);

7-cyclohexyloxycarbonylbenzo-1,2,3-thiadiazole (Compound 1.135);

7-(1-phenethyloxycarbonyl)-benzo-1,2,3-thiadiazole (Compound 1.140);

7-(3-methoxybenzyl)-benzo-1,2,3-thiadiazole (Compound 1.144);

7-(ethylthiocarbonyl)-benzo-1,2,3-thiadiazole (Compound 2.2);

7-(n-propylthiocarbonyl)-benzo-1,2,3-thiadiazole (Compound 2.3);

7-(benzylthiocarbonyl)-benzo-1,2,3-thiadiazole (Compound 2.5);

7-carbamoylbenzo-1,2,3-thiadiazole (Compound 3.1);

7-N-phenylcarbamoylbenzo-1,2,3-thiadiazole (Compound 3.6);

N-(7-benzo-1,2,3-thiadiazoyl)-glycine (Compound 3.9);

7-(N-diallylcarbamoyl)-benzo-1,2,3-thiadiazole (Compound 3.26);

6-fluoro-7-methoxycarbonylbenzo-1,2,3-thiadiazole (Compound 7.6);

6-fluoro-7-carboxybenzo-1,2,3-thiadiazole (Compound 7.8);

5-fluoro-7-benzyloxycarbonylbenzo-1,2,3-thiadiazole (Compound 7.52);

5-fluoro-7-carboxybenzo-1,2,3-thiadiazole (Compound 7.59);

5-fluoro-7-ethoxycarbonylbenzo-1,2,3-thiadiazole (Compound 7.61).

Surprisingly, it has now been found that the compounds of formula I,used in accordance with the invention, prevent healthy plants from beingattacked by harmful microorganisms from the outset and thus protect theplants from the damage caused by such an attack. The great advantage ofthe method of treating plants according to the invention lies in thefact that instead of chemical substances acting directly on theplant-destructive microorganisms, the plant's own biological defencesystem is activated and stimulated before the plant is attacked, so thatit can be ensured that the treated plants remain healthy by virtue oftheir own resources without any further direct use of microbicidalsubstances during the vegetative period. It is therefore especiallycharacteristic of compounds of formula I that when they are used atenvironmentally safe application rates they do not act directly on theharmful organisms, but instead have an action immunising healthy plantsagainst plant diseases. In this connection it was not possible to detectany direct action against members of the most important groups of fungi(for example Fungi imperfecti, Oomycetes). Accordingly, the use of thecompounds of formula I according to the invention avoids disadvantageousside-effects, which otherwise are to be observed to a greater or lesserextent in the case of the direct control of parasites on plants by meansof chemical substances, and this has the advantageous result that thegrowth of the plants is completely undisturbed. Furthermore, in the caseof some of the novel compounds falling within the scope of formula I', amicrobicidal, especially phytofungicidal, activity can occur in additionto and independently of the plant-immunising activity.

The mode of action of the compounds of formula I that underlies theinvention has at the same time the aim of generally increasing thecapacity of the treated plants to defend themselves, so that a generalantimicrobial resistance to a broad spectrum of harmful microorganismsis thereby attained. The method according to the invention is thereforeparticularly suitable for practical uses. The systemic activity inherentin the compounds of formula I means that the protective action extendsalso to the parts of the treated plants that grow later.

The immunising method according to the invention is effective againstphytopathogenic fungi belonging to the following classes: Fungiimperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria,Cercospora and Alternaria); Basidiomycetes (e.g. the genera Hemileia,Rhizoctonia, Puccinia); and Ascomycetes (e.g. Venturia, Podosphaera,Erysiphe, Monilinia, Uncinula).

The immunising method can be used especially advantageously against thefollowing harmful organisms: fungi, for example Oomycetes (for examplePlasmopara viticola, Phytophthora infestans), Fungi imperfecti (forexample Colletotrichum lagenarium, Piricularia oryzae, Cercosporanicotinae), Ascomycetes (for example Venturia inaequalis); bacteria, forexample pseudomonads (Pseudomonas lachrymans, Pseudomonas tomato,Pseudomonas tabaci); xanthomonads (for example Xanthomonas oryzae,Xanthomonas vesicatoria), Erwinia (for example Erwinia amylovora); andviruses, for example the tobacco mosaic virus.

The method according to the invention can be used for the protection ofplants from different crops of useful plants.

Within the scope of the present invention the areas of indicationdisclosed herein apply e.g. to the following species of plants: cereals(wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugarbeet and fodder beet), pomes, drupes and soft fruit (apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries andblackberries), leguminous plants (beans, lentils, peas, soybeans), oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows,melons), fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges,lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae(avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts,coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants,as well as ornamentals (flowers, shrubs, deciduous trees and conifers).

This list does not constitute a limitation.

The following plants are to regarded as being particularly suitabletarget crops for the use of the method according to the invention:cucumbers, tobacco, vines, rice, cereals (for example wheat), pears,pepper, potatoes, tomatoes and apples.

The compounds of formula I can be prepared by the following processes:

1. compounds of formula Ia ##STR11## in which R, X, Y and U have themeanings given under formula I, are prepared by reacting:

1.1 compounds of formula II ##STR12## in which L' is a leaving group,for example halogen, O-acyl, for example the acyl radical belonging tothe symmetric anhydride of acid Ib, or 1-imidazoyl,

with compounds of formula III

    RUH                                                        (III)

a) in an excess of the reactant RUH or

b) in the presence of an organic base either with or without4-dialkylaminopyridine as catalyst in inert solvents or

c) in the presence of an inorganic base, the reaction in each case beingcarried out in a temperature range of from -10° to 180° C., preferablyfrom 0° to 100° C.; and

1.2 compounds of formula Ib ##STR13## with compounds of formula III inexcess or in an inert solvent in the presence of an acid, such assulfuric acid, hydrochloric acid, p-toluenesulfonic acid or borontrifluoride/diethyl ether complex, or in the presence ofdicyclohexylcarbodiimide at a temperature of from -10° to 180° C.,preferably from 0° to 140° C.; and

2. compounds of formula Ic ##STR14## in which the symbols R₁, R₂, X andY have the meanings given under formula I, are prepared by reacting:

2.1 compounds of formula II with compounds of formula IV ##STR15##

a) in an excess of the reactant HN(R₁)R₂ or

b) in the presence of an organic base either with or without4-dialkylaminopyridine as catalyst in inert solvents or

c) in the presence of an inorganic base, the reaction in each case beingcarried out in a temperature range of from -10° to 160° C., preferablyfrom 0° to 100° C.; and

3. compounds of formula Id ##STR16## in which A' is the radical U¹N(═C)_(n) (R₃)R₄ and X, Y, R₃, R₄, R₅ and n have the meanings givenunder formula I, are prepared by:

3.1 reacting compounds of formula Ie ##STR17## in which Z' is a groupCOOH, COCl, COOAlk¹ or an acyloxycarbonyl radical, for example ##STR18##benzoyloxycarbonyl or acetoxycarbonyl, wherein Alk1 is C₁ -C₄ alkyl, inthe presence of a base, with hydrazine derivatives of formula V or VI##STR19## in an inert solvent at a temperature of from -10° to 180° C.,preferably from 0° to 100° C.; or

3.2 reacting compounds of formula Ie stepwise first with hydrazine, andthen reacting the resulting hydrazine compounds

3.2.1 with the alkylating agent R₃ -L or R₄ -L in which L is a leavinggroup, in an inert solvent at a temperature of from 0° to 160° C.,preferably from 20° to 120° C.; or

3.2.2 with an aldehyde or ketone of formula R₃ (R₄)C=O in which R₃ andR₄ have the meanings given under formula I, with or without the additionof an organic or inorganic acid, at a temperature of from -10° to 150°C., preferably from 20° to 100° C., and subsequently, if desired,

3.2.3 with an alkylating agent L-R₅ in which L is a leaving group, inthe presence of a strong base in an inert solvent at a temperature offrom -80° to 120° C., preferably from -40° to 80° C.; or, if desired,

3.2.4a) hydrogenating the hydrazone derivatives prepared under (3.2.1)with hydrogen at a pressure of from 1 to 30×10⁵ Pa in the presence of acatalyst in admixture with activated carbon in an inert solvent at atemperature of from 0° to 100° C., or

3.2.4b) treating the hydrazone derivatives prepared under (3.2.1) with acomplex metal hydride, for example sodium cyanoborohydride, in an inertsolvent at a temperature of from -10° to 80° C., preferably from 0° to50° C.; and

4. compounds of formula If ##STR20## in which the symbols X and Y havethe meanings given under formula I, are prepared by

treating compounds of formula Ig [prepared according to process (2)]##STR21## with a dehydrating agent in an inert solvent or without asolvent at a temperature of from -10° to 250° C., suitable dehydratingagents being:

a) trifluoroacetic acid anhydride in the presence of a base, for examplepyridine, in an inert solvent, for example tetrahydrofuran or dioxane,at a temperature of from -10° to 40° C.; or

b) chlorosulfonyl isocyanate in an inert solvent, for exampletetrahydrofuran, at a temperature of from 0° to 65° C., with subsequenttreatment with dimethylformamide (see Org. Synth. 50, 18 of Chem. Ber.100, 2719); or

c) phosphorus pentoxide with or without an inert solvent, for example1,2-dichloroethane, xylene or chlorobenzene, optionally in a bomb tubeunder elevated pressure, at from 50° to 250° C. (see Fieser, Reagentsfor Organic Synthesis 1, 871);

5.1 compound of formula IL¹ ##STR22## in which R₃, R₄, X and Y have themeanings given under formula I, are prepared by reacting oximederivatives of formula

    HO--N═C(R.sub.3)R.sub.4

with activated acid derivatives of formula ##STR23## in which AKS is ahalogen, an O-acyl, for example the O-acyl radical of the free acid ofthe formula above, acetoxy or benzoyloxy, or 1-imidazolyl, in an inertsolvent and a base at from -20° C. to 120° C., preferably from 0° to 50°C., or by reacting the free acid (=Ib) in the presence ofdicyclohexylcarbodiimide under the same conditions (Lit. Ber. 83, 186(1950); Houben-Weyl E5, p. 773);

5.2 compounds of formula IL² ##STR24## in which R₃, R₄, X and Y have themeanings given under formula I, are prepared by reduction of compoundsof formula IL¹ ##STR25##

a) with a silane, for example triethylsilane, in the presence of anacid, for example trifluoroacetic acid, at from 0° to 80° C., or

b) with sodium cyanoborohydride in the presence of an organic acid, forexample acetic acid, at from 0° to 80° C., or

c) by catalytic methods, for example with Pt/H₂.

In a special synthesis method, compound of formula IL² in which R₃ andR₄ are hydrogen are prepared by reacting an acid halide or an acidanhydride of an acid of formula Ib ##STR26## withN,O-bis-trimethylsilylhydroxylamine in the presence of a base, forexample butyllithium, in an inert solvent at from -80° to 60° C.,preferably from -50° to 50° C.

The 7-carboxylic acid esters described in the above formulae in which Uis oxygen and R has the meanings given under formula I, provided theyare not radicals that contain OH groups or silicon- orphosphorus-containing groups, can be converted into one anotheraccording to transesterification methods described in the literature.

The precursor compounds of formulae Ib, Ie and II can be preparedaccording to known methods, for example within the scope of thefollowing synthesis: ##STR27## in which Y' is hydrogen, halogen, SO₃ H,SO₃ M or hydroxy;

X' is hydrogen, halogen, methyl, methoxy or COOH;

E^(a) is a readily removable group, for example hydrogen or C₁ -C₄alkyl, for example methyl, ethyl or isopropyl, or benzyl;

L is a halogen or nitro;

Z^(a) is a group COOH or COOC₁ -C₄ alkyl.

If Z^(a) is a free acid group (--COOH), this group can be convertedusing customary methods into an ester group, for example the methylester, into an acid halide, for example the acid chloride, or into thesymmetric or a mixed acid anhydride, for example with the acetyl orbenzoyl radical.

In a parallel method of synthesis there are prepared those compound offormula I represented by formula I'^(b) ##STR28## in which Z^(b) has themeanings of Z given under formula I provided they are not radicals thatcontain primary amino or secondary amino groups, UH or nitro groups,Si(C₁ -C₈ alkyl)₃ or phosphorus-containing groups, and X' and Y' havethe meanings given above under formula Ii^(a). ##STR29## in which E^(b)is a readily removable group, for example hydrogen, C₁ -C₁₆ alkyl, forexample methyl, ethyl, isopropyl, n-dodecyl, or benzyl or acyl, forexample acetyl or the sulfonic acid radical (--SO₃ H--) or cyano, or aspart of a disulfide bridge, is a second radical ##STR30## and L has themeaning given under formula VIII^(a).

Furthermore, compound of formula Ik ##STR31## can be prepared accordingto a special process (C) by diazotisation of a compound of formula XI'##STR32## in which X', E^(b) and Z^(b) have the meanings given aboveunder formula XI', in an acidic medium with a nitrite compound at from-40° to 30° C., and in the same reaction vessel or in a second reactionvessel treatment with a reducing agent at from -40° to 80° C.,preferably from -30° to 30° C., it being possible to add the reducingagent before, after or at the same time as the nitrite compound.

In a special form of process (C), Z^(b) in the above formulae XI' and Ikis an acid ester (COOR^(a)), X' is hydrogen and Ra has the same meaningsas R with the exception of radicals containing UH or nitro groups and ofsilicon- or phosphorus-containing radicals, compounds of formula##STR33## being prepared by diazotisation of compound of formula##STR34## in an acidic medium with a nitrite compound at a temperatureof from -20° to 30° C., and in the same reaction vessel reduction at atemperature of from -20° to 80° C., preferably from 20° to 30° C., itbeing possible to add the reducing agent before, after or at the sametime as the nitrite compound.

Using a further special process it is possible to prepare compounds offormula Ik' ##STR35## by diazotisation of a compound of formula XI'##STR36## in which X', E^(b) and Z^(b) have the meanings given aboveunder formula XI', in an acidic medium with a nitrite compound at from-40° to 30° C., and

a) reaction of the diazonium salt with a copper halide at a temperatureof from -30° to 180° C., or

b) if Hal is fluorine, treatment of the diazonium salt with hydrofluoricacid or tetrafluoroboric acid, optionally in the presence of copperfluoride salts (Lit. Houben-Weyl, 5/3, 216).

In process (C) described above, the acidic reaction medium used may bean aqueous dilution of an inorganic acid, such as, for example, ahydrohalic acid, phosphoric acid, sulfuric acid or hydrofluoroboricacid; it is, however, also possible to use suitable organic acids, towhich inert organic solvents, for example tetrahydrofuran or dioxane,may be added. Suitable nitrites are both inorganic nitrite compounds,for example the alkali metal and alkaline earth metal salts, and organicnitrite compounds, for example alkyl nitrites. Reducing agents may be,for example, alcohols, for example ethanol, or hypophosporous acid,metallic copper or trialkylsilanes, for example triethylsilane, andferrocyanides or ferrocenes, for example decamethylferrocene. Thereduction step can, if desired, be carried out in the presence offurther additives, for example Crown ethers or polyethylene glycol.

The described method (C) is a novel process of a chemically uniquenature with which it is possible to obtain fused thiadiazole compoundsin an advantageous manner.

The synthesis of the precursors of compound XI' ##STR37## is carried outby reacting compounds of formulae VIII', VIII" and IX ##STR38## in whichformulae the substituents have the following meanings: X' is hydrogen,halogen, methyl, methoxy or COOH;

E^(a) is a readily removable group, for example hydrogen, C₁ -C₄ alkyl,for example methyl, ethyl or isopropyl, or benzyl;

E^(b) is a readily removable group, for example hydrogen, C₁ -C₁₆ alkyl,for example methyl, ethyl, isopropyl, n-dodecyl, or benzyl or acyl, forexample acetyl or the sulfonic acid radical (--SO₃ H--) or cyano or, aspart of a disulfide bridge, is a second radical ##STR39## L is halogenor nitro; L' is a leaving group, for example halogen, O-acyl, forexample the acyl radical belonging to the symmetric anhydride of theacid Ib, or 1-imidazoyl;

Z^(a) is a group COOH or COOC₁ -C₄ alkyl;

Z^(b) has the meanings of Z given under formula I provided they are notradicals that contain primary or secondary amino groups, nitro or UHgroups, Si(C₁ -C₈ alkyl)₃ or phosphorus-containing groups; withcompounds of the formulae HS-E^(a) or HS-E^(b) in the presence of abase, for example an alkali metal carbonate (for example Na₂ CO₃ or K₂CO₃) or an alkaline earth metal carbonate (for example MgCO₃), alkoxides(for example sodium alcoholates or potassium tert.-butoxide), or alkalimetal hydrides (for example sodium hydride), in an inert, preferablydipolar aprotic solvent (for example dimethyl sulfoxide,dimethylformamide, hexamethlphosphoric acid triamide,N-methylpyrrolidone, acetonitrile, dioxane or tetrahydrofuran) at atemperature of from -10° to 120° C., preferably from 0° to 60° C., toform compounds of formula X' ##STR40## which are converted into thecompounds of formula XI' ##STR41## by either catalytic or metallicreduction.

For the catalytic reduction it is possible to use, for example, Raneynickel and palladium, platinum or rhodium catalysts; the reduction canbe carried out under normal pressure or slightly elevated pressure at atemperature of from 0° to 150° C. Suitable solvents are, for example,tetrahydrofuran or dioxane.

For the metallic reduction it is possible to use, for example,iron/hydrochloric acid, iron/acetic acid, tin/hydrochloric acid,zinc/hydrochloric acid, zinc/acetic acid, copper/formic acid.

Further suitable reducing agents are tin(II) chloride/hydrochloric acid,nickel/hydrazine, titanium trichloride, alkali metal sulfides or sodiumdithionite. The reduction can be carried out at a temperature of from 0°to 120° C., and water or alcohols, for example methanol, ethanol,n-propanol or isopropanol, can be used as solvents.

Furthermore, if Z^(a) is the acid function (--COOH), it is possible toprepare special derivatives of formula IX in which Z^(b) is a radical--COUR'--, --CON(R₁)R₂ or --CON(R₅)N(R₃)R₄, by

a) reacting, in a known manner, the derivative of formula VIII^(a)(Y'=NO₂) synthesised first, with an alcohol of formula HUR' or an amineof formula HN(R₁)R₂ or with a hydrazide of formula HN(R₅)N(R₃)R₄ in thepresence of a suitable base, optionally catalysed by the addition ofdimethylaminopyridine, in an inert solvent at a temperature of from -20°to 170° C., preferably from 0° to 110° C., or

b) reacting a compound of formula VIII' (Z^(a) =COOH) in the presence ofdicyclohexylcarbodiimide with an alcohol of formula HUR' or with anamine of the formula HN(R₁)R₂ or with a hydrazide of formulaHN(R₅)N(R₃)R₄ in an inert solvent at a temperature of from 0° to 120°C., preferably from 10° to 80° C.

the meanings of the radicals R₁ to R₅ and the symbol U have already beendescribed in the text above and R' has the same meaning as R with theexception of the radicals (T)-P(O)(OR₆)-(C₁ -C₄ alkyl), (T)-PO(OR₆)₂ and(T)_(n) -Si(C₁ -C₈ alkyl)₃.

The compounds of formula XI' are novel and form part of the presentinvention: ##STR42## wherein X' is hydrogen, halogen, methyl, methoxy orCOOH;

E^(a) is a readily removable group, for example hydrogen, C₁ -C₄ alkyl,for example methyl, ethyl or isopropyl, or benzyl;

E^(b) is a readily removable group, for example hydrogen, C₁ -C₁₆ alkyl,for example methyl, ethyl, isopropyl, n-dodecyl, or benzyl or acyl, forexample acetyl or the sulfonic acid radical (--SO₃ H--) or cyano or, aspart of a disulfide bridge, is a second radical ##STR43## Z^(a) is agroup COOH or COOC₁ -C₄ alkyl; Z^(b) has the meanings of Z given underformula I provided they are not radicals that contain primary orsecondary amino groups, UH or nitro groups, Si(C₁ -C₈ alkyl)₃ orphosphorus-containing groups.

Compounds of formula XI' have microbicidal activity, especially againstphytopathogenic fungi and bacteria.

The compounds of formula X' are known or can be prepared according toprocesses known in the literature. Some of these derivatives can beprepared in accordance with a special process as follows:

Compounds of formula ##STR44## are first reacted in the presence of 2equivalents of a base, for example an alkali metal carbonate (forexample Na₂ CO₃ or K₂ CO₃) or an alkaline earth metal carbonate (forexample MgCO₃) or a metal hydride (for example NaH or LiH), with acompound of formula HS-E^(a) or HS-E^(b) in an inert, preferably dipolaraprotic solvent, for example dimethyl sulfoxide, dimethylformamide,hexamethylphosphonic acid triamide or N-methylpyrrolidone, and theresulting derivative is esterified with an alkylating agent R^(a) -L" inwhich L" is a leaving group, for example halogen, preferably iodine, or--OSO₂ R^(a) in which R^(a) -L" can be, for example, dimethyl sulfate:##STR45##

In the above formulae, R^(a) is an aliphatic or araliphatic radicaldefined under R for formula I and the radicals L, S-E^(a), S-E^(b) andX' have the meanings given under formulae VIII', VIII" and IX.

In the processes described above, unless indicated otherwise bases areto be understood as being both inorganic and organic bases. Theseinclude, as inorganic bases, for example, hydroxides, hydrogencarbonates, carbonates and hydrides of lithium, sodium, potassium,calcium and barium, and alkali metal amides, for example NaNH₂ oralkyllithium compounds, for example n-butyllithium. Examples of organicbases that may be mentioned are: amines, especially tertiary amines, forexample trimethylamine, triethylamine, tripropylamine, tributylamine,tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine,N,N-dimethylaniline, N,N-dimethyltoluidine,N,N-dimethyl-p-aminopyridine, N-methylpyrrolidine, N-methylpiperidine,N-methylpyrrolidine, N-methylimidazole, N-methylpyrrole,N-methylmorpholine, N-methylhexamethyleneimine, pyridine, quinoline,α-picoline, β-picoline, isoquinoline, pyrimidine, acridine,N,N,N',N'-tetramethylethylenediamine,N,N,N',N'-tetraethylethylenediamine, quinoxaline,N-propyldiisopropylamine, N,N-dimethylcyclohexylamine, 2,6-lutidine,2,4-lutidine or triethylenediamine.

Examples of inert solvents that may be used in accordance with theparticular reaction conditions are: halogenated hydrocarbons, especiallychlorinated hydrocarbons, for example tetrachloroethylene,tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane,chloroform, chloronaphthalene, dichloronaphthalene, carbontetrachloride, trichloroethane, trichloroethylene, pentachloroethane,difluorobenzene, 1,2-dichloroethane, 1,1-dichloroethane,1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene,iodobenzene, dichlorobenzene, dibromobenzene, chlorotoluene,trichlorobenzene; ethers, for example ethyl propyl ether, methyltert.-butyl ether, n-butyl ethyl ether, di-n-butyl ether, diisobutylether, diisoamyl ether, diisopropyl ether, anisole, phenetol, cyclohexylmethyl ether, diethyl ether, ethylene glycol dimethyl ether,tetrahydrofuran, dioxane, thioanisole, dichlorodiethyl ether,methylcellosolve; alcohols, for example methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol; nitrohydrocarbons, for examplenitromethane, nitroethane, nitrobenzene, chloronitrobenzene,o-nitrotoluene; nitriles, for example acetonitrile, butyronitrile,isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic orcycloaliphatic hydrocarbons, for example heptane, pinane, nonane, cymol,petroleum fractions within a boiling point range of from 70° to 190° C.,cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane,ligroin, trimethylpentane, trimethylpentane, 2,3,3-trimethylpentane,octane; esters for example ethyl acetate, acetoacetic acid esters,isobutyl acetate; amides, for example formamide, methylformamide,dimethylformamide; ketones, such as acetone, methyl ethyl ketone, andoptionally also water. Mixtures of the mentioned solvents and diluentsare also suitable.

The preparation methods described above, where they are not novel, arebased on known synthesis methods that can be found in the followingliterature:

The Chemistry of Heterocyclic Compounds with Nitrogen and Sulfur orNitrogen, Sulfur and Oxygen, Interscience Publ., New York 1952; P. Kirbyet al., J. Chem. Soc. (C) 321 (1967) and 2250 (1970) and 3994 (1971);FR-PS 1 541 415; J. Org. Chem. 27, 4675 (1962); GermanOffenlegungsschriften Nos. 2 400 887 and 2 504 383; SU-PS 400 574 [Chem.Abstr. 80(9)47661 h]; Org. Synth. Coll. Vol. I, 125; Tetrahedr. 21, 663(1965).

The compounds of formulae X, X', XI and XI' are novel substances, whilstsome of the compounds of formulae VIII, VIII' and IX are novel. Thenovel compounds form part of the present invention.

The plant-protective compositions used within the scope of the inventionwhich contain compounds of formula I as active ingredients are likewiseto be regarded as forming part of the invention.

The compounds of formula I are normally applied in the form ofcompositions and can be applied to the plant or to the locus thereof,simultaneously or in succession, with further compounds. These compoundscan be fertilisers or micronutrient donors or other preparations thatinfluence plant growth. They can also be selective herbicides,insecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or application-promoting adjuvantscustomarily employed in the art of formulation.

Suitable carriers and adjuvants can be solid or liquid and correspond tothe substances ordinarily employed in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula I, or anagrochemical composition which contains at least one of said compounds,is foliar application. However, the compounds of formula I can alsopenetrate the plant through the roots via the soil (systemic action) ifthe locus of the plant is impregnated with a liquid formulation, or ifthe compounds are applied in solid form to the soil, e.g. in granularform (soil application). The compounds of formula I may, however, alsobe applied to seeds (coating) by impregnating the seeds either with aliquid formulation containing a compound of formula I, or coating themwith a solid formulation (dressing). Furthermore, in some cases othermethods of application may be possible, for example the specifictreatment of the plant stem or buds.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation, and are for this purpose formulated in known manner e.g.into emulsifiable concentrates, coatable pastes, directly sprayable ordilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering, coatingor pouring, are chosen in accordance with the intended objectives andthe prevailing circumstances. Advantageous rates of application arenormally from 50 g to 5 kg of active ingredient (a.i.) per hectare,preferably from 100 g to 2 kg a.i./ha, most preferably from 100 g to 600g a.i./ha.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound (active ingredient) of formula I and, whereappropriate, a solid or liquid adjuvant, are prepared by homogeneouslymixing and/or grinding the active ingredients with extenders, e.g.solvents, solid carriers and, where appropriate, surface-activecompounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils, such as epoxidised coconut oil or soybeanoil; or water.

The solid carriers used e.g. for dusts and dispersible powders, arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are, for example, calciteor sand. In addition, a great number of pregranulated materials ofinorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues. Particularly advantageousapplication-promoting adjuvants are also natural (animal or vegetable)or synthetic phospholipids of the series of the cephalins and lecithins.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals.

Both so-called water-soluble soaps and also water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid or ofnatural fatty acid mixtures which can be obtained e.g. from coconut oilor tallow oil.

Synthetic surfactants that may be used are especially fatty alcoholsulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivativesor alkylsulfonates. The fatty alcohol sulfonates or sulfates are usuallyin the form of alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts and contain a C₈ -C₂₂ alkaliradical.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

The compositions may also contain further auxiliaries such asstabilisers, antifoams, viscosity regulators, binders, tackifiers aswell as fertilisers or other active ingredients for obtaining specialeffects.

The agrochemical compositions usually contain 0.1 to 99% by weight,preferably 0.1 to 95% by weight, of a compound of formula I, 99.9 to 1%by weight, preferably 99.8 to 5% by weight, of a solid or liquidadjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of asurfactant.

The Examples which follow serve to illustrate the invention in moredetail but do not constitute a limitation thereof.

1. PREPARATION EXAMPLES Example 1.1 Preparation of2-chloro-3-nitrobenzoic acid methyl ester (intermediate) ##STR46##

50.0 g (0.248 mol) of 2-chloro-3-nitrobenzoic acid are dissolved in 500ml of methanol, and 20 ml of concentrated sulfuric acid are addedthereto. After refluxing for 24 hours, the mixture is poured ontoice/water and the white precipitate is isolated by filtration, washedwith water and dried.

Yield: 53 g (99% of the theoretical yield); m.p. 68° C.

Example 1.2 Preparation of 2-benzylthio-3-nitrobenzoic acid methyl ester(intermediate) ##STR47##

45.4 g (0.21 mol) of 2-chloro-3-nitrobenzoic acid methyl ester and 24.8ml (0.21 mol) of benzyl mercaptan are dissolved in 420 ml ofdimethylformamide, and then 29.2 g (0.21 mol) of potassium carbonate areadded and the batch is stirred for 8 hours at 80° C. It is then pouredonto ice/water and extracted twice with ethyl acetate. The extracts arewashed with water, dried over magnesium sulfate and concentrated byevaporation.

Yield: 62.7 g (98.5% of the theoretical yield) oil.

Example 1.3 Preparation of 3-amino-2-benzylthiobenzoic acid methyl ester(intermediate) ##STR48##

62.7 g (0.207 mol) of 2-benzylthio-3-nitrobenzoic acid methyl ester aredissolved in 700 ml of tetrahydrofuran, 14 g of Raney nickel are addedand the batch is hydrogenated at 20°-28° C.

Yield: 54.5 g (96% of the theoretical yield).

Example 1.4 Preparation of 5-bromo-2-chloro-3-nitrobenzoic acid methylester (intermediate) ##STR49##

20 ml of concentrated sulfuric acid are added dropwise to 51.0 g (0.182mol) of 5-bromo-2-chloro-3-nitrobenzoic acid and 500 ml of methanol. Themixture is then boiled under reflux for 16 hours and subsequently cooledwith an ice bath and the resulting precipitate is isolated byfiltration. The mother liquor is concentrated, water is added and theresulting precipitate is isolated by filtration.

Yield: 50.2 g (94% of the theoretical yield), m.p. 69° C.

Example 1.5 Preparation of 2-benzylmercapto-5-bromo-3-nitrobenzoic acidmethyl ester (intermediate) ##STR50##

71.6 g (0.58 mol) of benzyl mercaptan are dissolved in 2.9 l ofmethanol/water (8:2), and 79.8 g (0.58 mol) of potassium carbonate areadded. At 0°-5° C., 170 g (0.58 mol) of 5-bromo-2-chloro-3-nitrobenzoicacid methyl ester are added in portions over a period of 2.5 hours withstirring. Stirring is then continued for a further 2 hours and theinternal temperature is then raised to 20° C. The resulting precipitateis then isolated by filtration, washed with a small amount of water andsubsequently with 500 ml of methanol/water. After drying, 208 g (94%) ofpale yellow product are obtained. Recrystallisation from 400 ml ofmethanol gives 190 g (86% of the theoretical yield) of product having amelting point of 65°-66° C.

Example 1.6 Preparation of 3-amino-2-benzylthiobenzoic acid methyl ester(intermediate) ##STR51##

156.25 g (0.408 mol) of 2-benzylthio-5-bromo-3-nitrobenzoic acid methylester are hydrogenated in 3 l of tetrahydrofuran in the presence of 60 gof Pd/C (5%). After the reduction of the nitro group, a further 30 g ofPd/C (5%) and 45.4 g (0.448 mol) of triethylamine are added andhydrogenation is continued. The catalyst is then isolated by filtrationand the solution is concentrated. The oily residue is taken up in ethylacetate, washed three times with water, dried over magnesium sulfate andfiltered, and the solution is concentrated by evaporation. The resultingproduct (111 g) is further processed directly.

Example 1.7 Preparation of 7-methoxycarbonylbenzo-1,2,3-thiadiazole##STR52##

475 g (1.74 mol) of 3-amino-2-benzylthiobenzoic acid methyl ester areslowly added at 35° C. to 1.18 l of concentrated hydrochloric acid in520 ml of water to form the hydrochloride. The batch is stirred for 15minutes at that same temperature and is then cooled to -5° C. A solutionof 120 g of sodium nitrite in 520 ml of water is then added dropwiseover a period of 2.5 hours. When the dropwise addition is complete, thebatch is stirred for 2 hours at 0° and for a further 2 hours at 20° C.The reaction material is isolated by filtration, washed with water andpressed off. Recrystallisation from ethyl acetate/hexane gives 292 g(86% of the theoretical yield) of product having a melting point of134°-135° C.

Example 1.8 Preparation of benzo-1,2,3-thiadiazole-7-carboxylic acid##STR53##

100 g (0.51 mol) of 7-methoxycarbonylbenzo-1,2,3-thiadiazole aresuspended in 1000 ml of water, and then 310 ml of 2N sodium hydroxidesolution and 5 ml of dioxane are added. The reaction mixture is heatedto 40° C., is stirred for 4 hours at that temperature and is then cooledto 10° C. A further 1000 ml of water are added and the batch isneutralised with 310 ml of 2N hydrochloric acid. The resultingprecipitate is isolated by filtration, lightly dried in a current of airand then dissolved in tetrahydrofuran and the solution is dried overmagnesium sulfate, filtered and concentrated. The crystals are suspendedin hexane, isolated by filtration and dried.

Yield: 91 g (98% of the theoretical yield); m.p. 261°-263° C.

Example 1.9a Preparation of benzo-1,2,3-thiadiazole-7-carboxylic acidchloride (intermediate) ##STR54##

12.54 g (0.070 mol) of benzo-1,2,3-thiadiazole-7-carboxylic acid aremixed with 80 ml of thionyl chloride. The mixture is heated andmaintained at a bath temperature of 90° C. for 8 hours. The excessthionyl chloride is then removed by distillation in a rotary evaporatorat a bath temperature of 40° C. The resulting oil solidifies; m.p. 107°C.

For further reactions, the acid chloride obtained is dissolved intoluene and used further directly.

Example 1.9b Preparation of the symmetrical anhydride of1,2,3-benzothiadiazole-7-carboxylic acid ##STR55##

3 g of 1,2,3-benzothiadiazole-7-carboxylic acid are boiled under refluxin 50 ml of acetic anhydride for 24 hours. The thin suspension is thenconcentrated by evaporation in vacuo, and the solid residue is suspendedin ether and isolated by filtration to give 4.3 g of anhydride having amelting point of 117°-119° C. The same compound is also obtained, forexample, by heating the carboxylic acid withbis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride in drytetrahydrofuran (see Synthesis 1981, 616).

Example 1.10 Preparation of 7-cyanobenzo-1,2,3-thiadiazole ##STR56##

4.0 g (0.022 mol) of benzo-1,2,3-thiadiazol-7-ylcarboxylic acid amideare dissolved in 35 ml of tetrahydrofuran, and 3.6 ml (0.045 mol) ofpyridine are added. The batch is then cooled to 3° C. and a solution of3.9 ml (0.028 mol) of trifluoroacetic acid anhydride in 12 ml oftetrahydrofuran is added dropwise. The reaction mixture is subsequentlystirred for 22 hours at room temperature and then poured onto ice/waterand extracted twice with ethyl acetate. The extracts are washed withwater, dried over magnesium sulfate and filtered through a layer ofsilica gel. Concentration by evaporation gives 3.5 g (99% of thetheoretical yield) of crystalline product having a melting point of119°-122° C.

Example 1.11 Preparation of benzo-1,2,3-thiadiazole-7-carboxylic acidhydrazide ##STR57##

9.7 g of 7-methoxycarbonylbenzo-1,2,3-thiadiazole are reacted for 19hours with 4.8 g of hydrazine hydrate in 30 ml of water at 50° C. andthen for a further 6 hours at 80°-90° C. The suspension is cooledslightly, filtered while hot and washed with water to give 8.8 g ofwhite crystals having a melting point of 270°-272° C.

Example 1.12 Preparation of2-(benzo-1,2,3-thiadiazole-7-carbonyl)-1-(α-methylpropylidene)-hydrazine##STR58##

21.5 g of benzothiadiazole-7-carboxylic acid hydrazide and 150 ml ofmethyl ethyl ketone are heated to 70° C. over a period of 8 hours in 150ml of glacial acetic acid. The reaction mixture is then concentrated byevaporation in vacuo, the residue is taken up in 1 l of dichloromethaneand the solution is washed twice with 700 ml of ice/water. It is thendried over sodium sulfate, filtered and concentrated by evaporation andthe residue is suspended in ethyl acetate, filtered and dried. Theproduct indicated above melts at 159°-162° C.

Example 1.13 Preparation of2-(benzo-1,2,3-thiadiazole-7-carbonyl)-1-(2'-n-butyl)-hydrazine##STR59##

10.5 g of 2-(benzo-1,2,3-thiadiazole-7-carbonyl)-1-(α-methylpropylidenehydrazine are dissolved in 150 ml of dimethylformamide and 100 ml ofmethylcellosolve and the solution is hydrogenated over 7 g ofplatinum/carbon at room temperature and at normal pressure. The catalystis then isolated by filtration and the product that remains afterconcentrating the filtrate by evaporation is chromatographed with ethylacetate on silica gel to give the product in the form of white crystalshaving a melting point of 148°-150° C.

Example 1.14 Preparation of 2-benzylthio-3,5-dinitro-benzoic acid methylester (intermediate) ##STR60##

332 g (2.40 mol) of potassium carbonate are introduced into 500 ml ofdimethylformamide and cooled to -5° C. 375 g (1.14 mol) of2-chloro-3,5-dinitrobenzoic acid (75% with 25% water; transport andstorage form) in 1.1 l of dimethylformamide are then added over a periodof 30 minutes, during which time the internal temperature is maintainedat from -5° to 4° C. 142 g (1.14 mol) of benzyl mercaptan are then addeddropwise at from 0° to 3° C. over a period of 2.5 hours. The temperatureis subsequently raised to 20° C. over a period of 16 hours. 170 g (1.2mol) of methyl iodide are then added dropwise at room temperature over aperiod of 5 hours. The reaction mixture is then stirred for 16 hours atroom temperature and afterwards poured onto 3 l of ice/water, stirredand filtered. The material obtained by filtering with suction is washedfour times with 700 ml of water each time and is hydrogenated in thenext stage while still damp (see Example 1.15). The dried product has amelting point of 113°-114° C.

Example 1.15 Preparation of 2-benzylthio-3,5-diamino-benzoic acid methylester (intermediate) ##STR61##

The 2-benzylthio-3,5-dinitrobenzoic acid methyl ester obtained in theprevious stage (see Example 1.14), which is still damp, is dissolved in2 l of tetrahydrofuran and hydrogenated at from 30° to 35° C. with theaddition of 3×40 g of Raney nickel. The catalyst is then removed byfiltration, the filtrate is concentrated and the residue is taken up inethyl acetate. After drying over magnesium sulfate and treating withactivated carbon and fuller's earth, the filtrate is concentrated andthe product is caused to crystallise by the addition of diethyl ether.Yield: 253 g (77% of the theoretical yield over three stages); m.p.84°-86° C.

Example 1.16 Preparation of 7-methoxycarbonylbenzo-1,2,3-thiadiazole##STR62##

a) 100 g (0.35 mol) of 2-benzylthio-3,5diaminobenzoic acid methyl esterare added in portions to 250 ml of concentrated hydrochloric acid and110 ml of water and stirred for 1.5 hours at room temperature. Themixture is then cooled to -5° C. and, over a period of 2.5 hours withstirring, a solution of 48.5 g (0.70 mol) of sodium nitrite in 210 ml ofwater is added dropwise. The stirring operation is continued for afurther 2 hours at 0° C. 190 ml of 50% hypophosphorous acid are thenadded dropwise over a period of 21/2 hours. The temperature is thenraised to 20° C. over a period of 19 hours. The resulting product isisolated by filtration, washed with water and dried. For purification,the product is dissolved in ethyl acetate/methylene chloride, filteredthrough silica gel, evaporated and crystallised by the addition ofhexane. Yield: 44.4 g (65% of the theoretical yield); m.p. 132° C.

b) 576 g (2 mol) of 3,5-diamino-2-benzylthiobenzoic acid methyl esterare dissolved in 500 ml of 1,4-dioxane and the batch is added dropwiseto 5N hydrochloric acid (3 l) with stirring and cooling to from 0° to 5°C. The fine suspension is then cooled to from -17° to -20° C. and 294 gof sodium nitrite in 500 ml of water are added dropwise below thesurface over a period of 1.25 hours. While continuing to stir, theinternal temperature is raised to -5° C. over a period of 1 hour andmaintained for 2 hours. The suspension is then cooled to -15° C. andintroduced in portions, with stirring, into hypophosphorous acid (1.1 l)cooled to from -10° to -15° C., during which operation nitrogen isevolved. When the addition is complete, the internal temperature israised to room temperature over a period of 5-6 hours, the precipitateformed is isolated by filtration and stirred with 2.5 l of methylenechloride, and the portion that has not dissolved is again isolated byfiltration and the filtrate is separated from the water. The organicphase is then dried over sodium sulfate, stirred with 300 g of silicagel, filtered again and washed with methylene chloride, and the filtrateis concentrated by evaporation. Recrystallisation from methanol gives atotal of 244.8 g (63.1% of the theoretical yield) of beige crystalshaving a melting point of 130°-133° C.

c) 183 g (0.5 mol) of 3,5-diamino-2-n-dodecylthiobenzoic acid methylester, dissolved in 200 ml of dioxane, are added dropwise with coolingand stirring at 0°-5° C. to 1.2 l of 5N hydrochloric acid. Stirring iscontinued for approximately 1 hour to obtain a fine precipitate. Thebatch is then cooled to from -15° to -21° C. and a solution of 73.5 g ofsodium nitrite in 130 ml of water is added dropwise below the surfaceover a period of 1 hour while continuing to stir at that temperature.The internal temperature is then raised to -5° C. over a period of 1hour and stirring is continued for a further 3 hours at thattemperature. The suspension is then cooled to -10° C. again and is addedin portions over a period of 1.5 hours to hypophosphorous acid (280 ml),which is likewise cooled, during which operation nitrogen is evolved.Finally, stirring is continued for 6 hours during which time roomtemperature is reached, and then the precipitate is isolated byfiltration and is worked up as described under 1.16b to form the crudeproduct. For further purification, the latter can also be filteredthrough a suction filter filled with silica gel and then washed withmethylene chloride/hexane (10:1 ). The batch is concentrated byevaporation and the residue is stirred with 300 ml of methanol to give46.3 g of beige crystals. A further 7.2 g of crude product can beobtained from the filtrate after crystallisation from ethyl acetate,thus giving a total yield of 53.5 g (55.2% of the theoretical yield),m.p. 130°-133° C.

d) 1.48 g of 1,2,3-benzothiadiazole-7-carboxylic acid are introducedinto 40 ml of absolute tetrahydrofuran under a nitrogen atmosphere, and1.46 g of 1-chloro-N,N-2-trimethylpropenylamine are added dropwise at0°-3° C. with cooling. The batch is stirred overnight at roomtemperature, cooled again the day after, and a solution of 1.18 g ofpyridine and 0.64 g of absolute methanol is added dropwise thereto. Thebatch is then stirred for 7 hours at room temperature, diluted withmethylene chloride, and ice/water is added. The organic phase isseparated off, the aqueous phase is extracted three times with methylenechloride, and the extracts are washed with water, dried and concentratedby evaporation. The crystalline residue is dried at 50° C. under a highvacuum, triturated with a small amount of hexane and filtered and theprecipitate is washed thoroughly with hexane to give 1.38 g (87% of thetheoretical yield) of pure product having a melting point of 128°-130°C.

e) Using the same method as described in Example 1.16b,3,5-diamino-2-methylthiobenzoic acid methyl ester is converted into thetitle compound.

Example 1.17 Preparation of7-(2-trimethylsilylethoxycarbonyl)-benzo-1,2,3-thiadiazole ##STR63##

1.99 g (0.01 mol) of 7-benzothiadiazolecarboxylic acid chloride in 18 mlof toluene are added dropwise over a period of 25 minutes to a solutionof 1.9 ml (0.013 mol) of 2-trimethylsilylethanol, 2.4 ml (0.017 mol) oftriethylamine and 18 ml of toluene. The reaction mixture is then stirredfor 16 hours at room temperature and afterwards poured onto ice/waterand extracted twice with ethyl acetate. The extracts are combined,washed with water, dried over magnesium sulfate, filtered andconcentrated and the same amount of hexane is added and the batch isfiltered through silica gel. Concentration gives 2.0 g (71% of thetheoretical yield) of product; m.p. 37°-39° C.

Example 1.18 Preparation of7-(carbonyloxymethyl-O-ethyl-methylphosphinic acidester)-benzo-1,2,3-thiadiazole ##STR64##

2.6 g (0.013 mol) of benzo-1,2,3-thiadiazole-7-carboxylic acid chloridein 26 ml of dioxane are added dropwise to a solution of 2.2 g ofhydroxymethyl-methyl-phosphinic acid ethyl ester, 3.2 ml (0.023 mol) oftriethylamine and 26 ml of dioxane. The reaction mixture is then stirredfor 16 hours at room temperature and afterwards filtered through a layerof silica gel and concentrated. The product is recrystallized from ethylacetate/hexane.

Yield: 2.2 g (56%); m.p. 89°-92° C.

Example 1.19 Preparation of2-(benzo-1,2,3-thiadiazole-7-carbonyl-1-(2'-butyl)-hydrazine ##STR65##

10.5 g of 2-(benzo-1,2,3-thiadiazole-7-carbonyl)-1-(α-methylpropylidenehydrazine are dissolved in 150 ml of dimethylformamide and 100 ml ofmethylcellosolve and hydrogenated over 7 g of platinum/carbon at roomtemperature and at normal pressure. The catalyst is then isolated fromthe solution by filtration and the product remaining after concentratingthe filtrate by evaporation is chromatographed on silica gel (ethylacetate). The product is obtained in the form of white crystals having amelting point of 148°-150° C.

Example 1.20 Preparation of2-(benzo-1,2,3-thiadiazole-7-carbonyl-1-(2'-butyl)-hydrazine ##STR66##

4.8 g of benzo-1,2,3-thiadiazole-7-carboxylic acid hydrazide aredissolved in 300 ml of tetrahydrofuran, and 9.3 g of methyl ethyl ketoneand 0.6 g of 5% platinum/carbon catalyst are added. The batch is thenhydrogenated at from 20° to 25° C. at normal pressure until the reactionstops, during which time three further additions of catalyst of 2 g eachare made. The catalyst is then isolated by filtration, and the filtrateis concentrated by evaporation and recrystallised from ethyl acetate togive white crystals having a melting point of 147°-150° C.

Example 1.21 Preparation of 2-benzylthio-3-nitrobenzoic acid(intermediate) ##STR67##

6.85 g (0.055 mol) of benzyl mercaptan are dissolved in 150 ml ofdimethylformamide. The batch is then cooled to 0° C. and 15.2 g (0.11mol) of potassium carbonate are added. 10.6 g (0.050 mol) of2,3-dinitrobenzoic acid are then added in portions at from 0° to 5° C.and the internal temperature is afterwards raised to room temperatureover a period of 24 hours. The reaction mixture is then poured ontoice/water and acidified with hydrochloric acid. The resulting product isfiltered, washed with water and dried. Yield: 11.8 g (82% of thetheoretical yield); m.p. 152°-153° C.

Example 1.22 Preparation of 3-amino-2-benzylthiobenzoic acid ##STR68##

11.0 g (0.038 mol) of 2-benzylthio-3-nitrobenzoic acid are dissolved in110 ml of tetrahydrofuran and hydrogenated at from 20° to 25° C. in thepresence of Raney nickel at normal pressure. The catalyst is thenisolated by filtration, the filtrate is concentrated and the resultingproduct is used directly in the next stage (Example 1.23).

Example 1.23 Preparation of benzo-1,2,3-thiadiazole-7-carboxylic acid##STR69##

The product obtained in Example 1.22 is reacted analogously to Example1.7 with hydrochloric acid and sodium nitrite to give the title compoundwhich has a melting point of 260°-262° C.

Example 1.24 Preparation of 3,5-dinitro-2-isopropylthiobenzoic acidmethyl ester ##STR70##

33.2 g (0.240 mol) of potassium carbonate are introduced into 100 ml ofdimethylformamide and cooled to -5° C. 37.5 g (0.114 mol) of2-chloro-3,5-dinitrobenzoic acid (75% with 25% water) in 110 ml ofdimethylformamide are then added over a period of 20 minutes, duringwhich time the internal temperature is maintained at from -7° to -3° C.11.0 ml (0.114 mol) of isopropyl mercaptan (97%) in 20 ml ofdimethylformamide are then added dropwise at from -8° to -1° C. over aperiod of 45 minutes. The batch is then stirred for one hour at 0° C.and the temperature is then raised to 25° C. over a period of 24 hours.7.5 ml (0.12 mol) of methyl iodide are then added dropwise at roomtemperature over a period of 30 minutes. The reaction mixture issubsequently stirred for 16 hours at room temperature and then pouredonto 500 ml of ice/water, stirred and filtered. The material obtained byfiltering with suction is washed with water and dried at roomtemperature.

Yield: 32.6 g (95% of the theoretical yield); m.p. 62°-63° C.

Example 1.25 Preparation of 3,5-diamino-2-isopropylthiobenzoic acidmethyl ester ##STR71##

26.6 g (0.0886 mol) of 3,5-dinitro-2-isopropylthiobenzoic acid methylester are dissolved in 270 ml of tetrahydrofuran and hydrogenated withthe addition of 10 g of Raney nickel at from 30° to 35° C. The catalystis then isolated by filtration, the filtrate is concentrated and theresidue is crystallised from ethyl acetate/hexane.

Yield: 20.1 g (94% of the theoretical yield); m.p. 109°-111° C.

Example 1.26 Preparation of 7-methoxycarbonylbenzo-1,2,3-thiadiazole##STR72##

17.0 g (0.0707 mol) of 3,5-diamino-2-isopropylthiobenzoic acid methylester are added in portions to 100 ml of concentrated hydrochloric acidand 50 ml of water and the batch is stirred for one hour at roomtemperature. It is then cooled to -5° C. and a solution of 9.80 g (0.142mol) of sodium nitrite in 20 ml of water is added dropwise with stirringover a period of 2 hours. Stirring is continued for a further 2 hours at0° C. and then 23 ml (0.21 mol) of 50% hypophosphorus acid are addeddropwise over a period of 30 minutes. The temperature is then raised to20° C. over a period of 24 hours. 150 ml of water are added to thereaction mixture, and the product is isolated by filtration, washed withwater and dried. For purification, the product is taken up in 300 ml ofethyl acetate, boiled under reflux and filtered while hot. Hexane isadded to the concentrated filtrate. The resulting product is isolated byfiltration and dried.

Yield: 7.5 g (55% of the theoretical yield); m.p. 130°-131° C.

Example 1.27 Preparation of 3,5-dinitro-2-ethylthiobenzoic acid ethylester ##STR73##

33.2 g (0.240 mol) of potassium carbonate are introduced into 100 ml ofdimethylformamide and cooled to -5° C. 37.5 g (0.114 mol) of2-chloro-3,5-dinitrobenzoic acid (75% with 25% water) dissolved in 120ml of dimethylformamide are then added over a period of 20 minutesduring which time the internal temperature is maintained at from -5° to0° C. 8.9 ml (0.12 mol) of ethyl mercaptan in 20 ml of dimethylformamideare then added dropwise at -8° C. over a period of 20 minutes. The batchis then stirred for one hour at that same temperature and afterwards thetemperature is raised to room temperature over a period of 19 hours. 9.0ml (0.12 mol) of ethyl bromide in 20 ml of dimethylformamide are thenadded dropwise over a period of 10 minutes and the reaction mixture issubsequently stirred for 24 hours at room temperature and then pouredonto 500 ml of ice/water, stirred and filtered. The material obtained byfiltering with suction is washed with water and then dried at roomtemperature in vacuo and in the presence of phosphorus pentoxide.

Yield: 28.7 g (84% of the theoretical yield); m.p. 80°-81° C.

Example 1.28 Preparation of 3,5-diamino-2-ethylthiobenzoic acid ethylester ##STR74##

25.9 g (0.0862 mol) of 3,5-dinitro-2-ethylthiobenzoic acid ethyl esterare dissolved in 260 ml of tetrahydrofuran and hydrogenated at 30°-35°C. in the presence of 10 g of Raney nickel. The catalyst is thenisolated by filtration, and the residue is taken up in ethyl acetate,dried over magnesium sulfate, filtered and concentrated.

Yield: 19.3 g (93% of the theoretical yield).

Example 1.29 Preparation of 5-fluoro-1,2,3-benzothiadiazole-7-carboxylicacid ethyl ester ##STR75##

18.7 g (0.078 mol) of 3,5-diamino-2-ethylthiobenzoic acid ethyl esterare introduced into 100 g of anhydrous hydrogen fluoride at from 0° to-12° C. 12.9 g (0.187 mol) of sodium nitrite are then metered in at from0° to 5° C. over a period of two hours and the reaction mixture isstirred for a further two hours. The diazonium solution is thentransferred into a Teflon-coated autoclave and heated to 146° C.therein. After the reaction, the hydrogen fluoride is removed bydistillation and the residue is taken up in methylene chloride. Afterwashing with sodium hydrogen carbonate solution and drying withmagnesium sulfate, the solution is filtered and concentrated. Theresulting crude product is purified over a column of silica gel(solvent: petroleum ether/diethyl ether 2:1).

Yield: 1.5 g of yellow crystals having a melting point of 68°-69° C.

Example 1.30 Preparation of 2-benzylthio-3,5-diamino-benzoic acid methylester ##STR76##

17.7 g of iron turnings are heated to 66° C. in 80 ml of acetic acid(5%) with thorough stirring. A solution of 12.0 g (0.034 mol) of2-benzylthio-3,5-dinitrobenzoic acid methyl ester in 20 ml oftetrahydrofuran is then slowly added dropwise. After cooling, the batchis neutralised with saturated sodium hydrogen carbonate solution andextracted three times with ethyl acetate. The extracts are washed withwater, dried over magnesium sulfate, filtered and concentrated.Crystallisation from diethyl ether gives 8.1 g (82% of the theoreticalyield) of product; m.p. 80°-82° C.

Example 1.31 Preparation of 3,5-diamino-2-methylthiobenzoic acid methylester ##STR77##

Using the method described in Example 1.30,3,5-dinitro-2-methylthiobenzoic acid methyl ester is reduced using ironturnings to give the title compound which has a melting point of102°-104° C.

The following compounds can be prepared in the same manner as describedin the Examples above.

In the Tables of Compounds, the associated symbols are used for thefollowing radicals: ##STR78##

The heterocycles described above may be substituted bylow-molecular-weight radicals, such as aliphatic radicals having up toand including 6 carbon atoms, or by halogen atoms or other radicals.

                                      TABLE 1                                     __________________________________________________________________________     ##STR79##                                                                    Comp.                                                                         no.   R                        Physical data                                  __________________________________________________________________________    1.1   H                        m.p. 262° C.                            1.2   CH.sub.3                 m.p. 134-135° C.                        1.3   C.sub.2 H.sub.5          m.p. 62-63° C.                          1.4   n-C.sub.3 H.sub.7        m.p. 36-38° C.                          1.5   i-C.sub.3 H.sub.7        m.p. 78-79° C.                          1.6   n-C.sub.4 H.sub.9        oil                                            1.7   s-C.sub.4 H.sub.9                                                       1.8   t-C.sub.4 H.sub.9                                                       1.9   n-C.sub.5 H.sub.11       m.p. 35-37° C.                          1.10  n-C.sub.6 H.sub.13                                                      1.11  n-C.sub.8 H.sub.17       m.p. 41-44° C.                          1.12  2-Bromoethyl                                                            1.13  2-Chloroethyl                                                           1.14  2-Fluoroethyl                                                           1.15  2-Cyanoethyl                                                            1.16  2-Methoxyethyl           m.p. 30-32° C.                          1.17  2-n-Butoxyethyl                                                         1.18  2-Allyloxyethyl                                                         1.19  2,2,2-Trichloroethyl                                                    1.20  3-Aethoxypropyl                                                         1.21  3-Acetylpropyl                                                          1.22  3-Chloropropyl(n)                                                       1.23  3-Bromopropyl(n)                                                        1.24  1-Chloroprop-2-yl                                                       1.25  1-Bromoprop-2-yl                                                        1.26  2,3-Dibromopropyl(n)                                                    1.27  2-Nitroethyl                                                            1.28  Cyclopropylmethyl        m.p. 46-48° C.                          1.29  1-Cyclopropyl-eth-1-yl   m.p. 57-60° C.                          1.30  Cyclohexylmethyl         m.p. 62-64° C.                          1.31  Cyclooctylmethyl                                                        1.32  3-Phenylpropyl           b.p. 150° C./0,01 torr                  1.33  2-Phenylethyl            m.p. 77-79° C.                          1.34  Benzyl                   m.p. 94-95° C.                          1.35  2-Chlorobenzyl           m.p. 126-127° C.                        1.36  3-Chlorobenzyl                                                          1.37  4-Chlorobenzyl           m.p. 106-108° C.                        1.38  4-Methylbenzyl                                                          1.39  4-Methoxybenzyl          m.p. 98-100° C.                         1.40  4-Nitrobenzyl                                                           1.41  2-(4-Methoxyphenyl)ethyl                                                1.42  2-Penoxyethyl            m.p. 60-62° C.                          1.43  2-(4-Chlorophenoxy)ethyl                                                1.44  Allyl                    m.p. 57-58° C.                          1.45  4-Pentenyl                                                              1.46  2-Propynyl               m.p. 129-130° C.                        1.47  3-Hexynyl                                                               1.48  3-Chloro-but-2-enyl                                                     1.49  Cyclopropyl                                                             1.50  Cyclopnetyl              m.p. 62-64° C.                          1.51  Cyclooctyl                                                              1.52  Phenyl                                                                  1.53  2-Chlorophenyl           m.p. 108-110° C.                        1.54  3-Bromophenyl            m.p. 121-123° C.                        1.55  3,4-Dichlorophenyl                                                      1.56  4-Chloro-2-methyl-phenyl                                                1.57  4-t-Butylphenyl          m.p. 142-144° C.                        1.58  3-Nitrophenyl                                                           1.59  4-Nitrophenyl            m.p. 214-216° C.                        1.60  3-Cyanophenyl            m.p. 181-183° C.                        1.61  3-Trifluoromethylphenyl  m.p. 107-109° C.                        1.62  3-N,N-Dimethylaminophenyl                                               1.63  2-Methoxycarbonyl-phenyl                                                1.64  3-iodo-prop-2-yn-yl                                                     1.65  CH.sub.2COOCH.sub.3                                                     1.66  CH.sub.2COOC.sub.2 H.sub.5                                              1.67  CH(CH.sub.3)COOCH.sub.3                                                 1.68  CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                         m.p. 118-122° C.                                                       (S)-enantiomer                                 1.69  CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                     1.70  3-N,N-Dimethylaminopropyl                                               1.71  NC(CH.sub.3).sub.2       m.p. 127-130° C.                        1.72                                                                                 ##STR80##               m.p. 125° C.                            1.73                                                                                 ##STR81##               m.p. 112-114° C.                        1.74  NC(CH.sub.3)CH.sub.2 OCH.sub.3                                          1.75  NC(CN)CONH.sub.2                                                        1.76  NC(CN)C.sub.6 H.sub.5                                                   1.77  NC(CN)CONHC.sub.2 H.sub.5                                               1.78  NC(CN)CONHCONHC.sub.2 H.sub.5                                           1.79  CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                          m.p. 26° C.                             1.80  CH.sub.2 CH.sub.2 OH     m.p. 76-79° C.                          1.81  3-Fluorobenzyl           m.p. 100-102° C.                        1.82  4-Trifluoromethylbenzyl                                                 1.83  CH.sub.2 CH.sub.2 Q.sub.21                                              1.84  CH.sub.2 CH.sub.2 Q.sub.41                                              1.85  CH.sub.2 CH.sub.2 Q.sub.24                                              1.86  Diacetone-D-glucos-3-yl  m.p. 121-123° C.                        1.87  2-Fluorobenzyl           m.p. 113-115° C.                        1.88  4-Fluorobenzyl           m.p. 107-109° C.                        1.89  4-Methylphenyl           m.p. 141-143° C.                        1.90  2-Methoxycarbonylphenyl  m.p. 120-122° C.                        1.91  2-Carboxyphenyl                                                         1.92  CH.sub.2 Q.sub.11                                                       1.93  CH.sub.2 Q.sub.12                                                       1.94  CH.sub. 2 Q.sub.13                                                      1.95  CH.sub.2 Q.sub.14                                                       1.96  CH.sub.2 Q.sub.21        m.p. 67° C.                             1.97  CH.sub.2 Q.sub.22                                                       1.98  CH.sub.2 Q.sub.23                                                       1.99  CH.sub.2 Q.sub.31                                                       1.100 CH.sub.2 Q.sub.32        m.p. 166-168° C.                        1.101 CH.sub.2 Q.sub.41        m.p. 91-93° C.                          1.102 CH.sub.2 Q.sub.42        m.p. 97-99° C.                          1.103 CH.sub.2 Si(CH.sub.3).sub.3                                                                            m.p. 59-67° C.                          1.104 CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3                                                                   m.p. 37-39° C.                          1.105 CH.sub.2 P(O)(CH.sub.3)OC.sub.2 H.sub.5                                                                m.p. 92° C.                             1.106 CH.sub.2 P(O)(OCH.sub.3).sub.2                                          1.107 CH.sub.2 CH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2                          1.108 CH.sub.2 CH.sub.2 P(O)(OCH.sub.3).sub.2                                                                m.p. 86-88° C.                          1.109 CH.sub.2 P(O)(CH.sub.3)OCH.sub.3                                        1.110 CH(CH.sub.3)P(O)(OCH.sub.3).sub.2                                       1.111 Si(CH.sub.3).sub.2 C(CH.sub.3).sub.2 CH(CH.sub.3).sub.2                 1.112 Na.sup.⊕             m.p. >250° C.                           1.113 K.sup.⊕              m.p. >250° C.                           1.114 (HN(C.sub.2 H.sub.5).sub.3).sup.⊕                                                                  m.p. 86-89° C.                          1.115 (H.sub.2 N(CH.sub.2 CH.sub.2 OH).sub.2).sup.⊕                                                      m.p. 130° C.                            1.116 CH.sub.2 -Naphth-1-yl    m.p. 123-125° C.                        1.117 CH.sub.2 Naphth-2-yl     m.p. 94-96° C.                          1.118 CH.sub.2 CH.sub.2 -Naphth-1-yl                                          1.119 1-Phenethyl              m.p. 50-52° C.                          1.120 2-Phenyl-prop-2-yl                                                      1.121 CH.sub.2 CH.sub.2 CN                                                    1.122 (2-Sulfamoyl)-benzyl     m.p. 198-200° C.                        1.123 CH.sub.2 CH.sub.2 SCH.sub.3                                             1.124 1,2,3,4-Di-O-isopropylideine-D-galactopyranos-6-yl                      1.125 1,2,5,6-Di-O-isopropylidine-D-mannit-3-yl                               1.126 1,2,5,6-Di-O-isopropyliden-α-D-allofuranos-3-yl                   1.127 D-Glucofuranos-3-yl                                                     1.128 D-Galactopyranos-6-yl                                                   1.129 D-Mannit-3-yl                                                           1.130 D-Allofuranos-4-yl                                                      1.131 Mannopyranos-1-yl                                                       1.132 2-Methyl-D-glucosid-6-yl                                                1.133 1,2,5,6-Tetraacetyl-D-galactopyranos-3-yl                               1.134 2,3,5-Tribenzylribofuranos-1-yl                                         1.135 Cyclohexyl               m.p. 44-46° C.                          1.136 CH.sub.2Q.sub.46         m.p. 116-118° C.                        1.137 2,6-Difluorobenzyl       m.p. 117-119° C.                        1.138 CH.sub.2CCl.sub.2 CF.sub.3                                                                             m.p. 71-73° C.                          1.139 2-Nitrobenzyl            m.p. 196-198° C.                        1.140 2-Methylbenzyl           m.p. 95-97° C.                          1.141 CH.sub.2 C(OCH.sub.3).sub.2 CH.sub.3                                    1.142 3-Methyl-2-nitrobenzyl   m.p. 143-145° C.                        1.143 Cycloheptyl              n.sub.D.sup.31 = 1,5787                        1.144 3-Methyoxybenzyl         m.p. 73-75° C.                          1.145 2,4-Dichlorobenzyl       m.p. 118-120° C.                        1.146 Q.sub.19                 m.p. 82-83° C.                          1.147 CH.sub.2CH(OH)CH.sub.2 OH                                                                              m.p. 75-77° C.                          1.148 CH.sub.2 CH(OH)CH.sub.2 OCH.sub.3                                       1.149 CH.sub.2 COC.sub.4 H.sub.9 (n)                                          1.150 Q.sub.20                 m.p. 83-84° C.                          1.151 CH.sub.2Q.sub.25         m.p. 113-116° C.                        1.152 CH.sub.2CH(OH)CH.sub.2 OCH.sub.3                                        1.153 CH.sub.2Q.sub.26                                                        1.154 CH.sub.2OCO(CH.sub.3).sub.3                                                                            m.p. 98-100° C.                         1.155 CH.sub.2CHOHCH.sub.2 OC.sub.2 H.sub.5                                   1.156 1/2Mg.sup.2⊕                                                        1.157 CH.sub.2 CH.sub.2Q.sub.16                                               1.158 CH.sub.2 CH.sub.2Q.sub.15                                               1.159 CH.sub.2 CH.sub.2Q.sub.42                                               1.160 CH.sub.2 CH.sub.2N(C.sub.2 H.sub.5).sub.2                               1.161 CH.sub.2 CH.sub.2Q.sub.46                                               1.162 CH.sub.2 CH.sub.2Q.sub.21                                               1.163 CH.sub.2 CH.sub.2Q.sub.11                                               1.164 4'-Trifluoromethoxy-benzyl                                              1.165 CH.sub.2 CH.sub.2Q.sub.22                                               1.166 CH(CH.sub.3)Q.sub.42                                                    1.167 CH.sub.2 CH.sub.2 CH.sub.2Si(CH.sub.3).sub.3                            1.168                                                                         4-Phenoxy-phenyl                                                                    m.p. 97-99° C.                                                   1.169                                                                         3-Diphenyl                                                                          m.p. 108-110° C.                                                 1.170 CH(CH.sub.3)Q.sub.41                                                    1.171                                                                         4-Benzyl-benzyl                                                                     m.p. 117-119° C.                                                 1.172 CH.sub.2 COCH.sub.3                                                     1.173 CH.sub.2 COC.sub.5 H.sub.11.sbsb.(n)                                    1.174 CH(CH.sub.3)Q.sub.21                                                    1.175 C(CH.sub.3).sub.2Q.sub.46                                               1.176 2-(OCF.sub.3)-phenyl                                                    1.177 3-(OCF.sub.2 CF.sub.3)-phenyl                                           1.178 2-Naphthyl               m.p. 136-137° C.                        __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR82##                                                                    Comp.                                                                         no.        R             Physical data                                        ______________________________________                                        2.1        CH.sub.3                                                           2.2        C.sub.2 H.sub.5                                                                             m.p. 87° C.                                   2.3        C.sub.3 H.sub.7 (n)                                                                         oil                                                  2.4        C.sub.4 H.sub.9 (n)                                                2.5        Benzyl        m.p. 101-104° C.                              2.6        Phenyl        m.p. 137-140° C.                              2.7        4-Chlorophenyl                                                                              m.p. 53--55° C.                               2.8        CH.sub.2 COOCH.sub.3                                                                        m.p. 126-129° C.                              2.9        CH.sub.2 COOC.sub.2 H.sub.5                                        2.10       4-Methylphenyl                                                     2.11       n-Hexyl                                                            2.12       Cyclohexyl                                                         2.13       Cyclopentyl                                                        2.14       H                                                                  2.15       Na.sup.⊕                                                       2.16       K.sup.⊕                                                        ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR83##                                                                    ______________________________________                                        Comp.                                                                         no.   NR.sup.1 R.sup.2      Physical data                                     ______________________________________                                        3.1   NH.sub.2              m.p. >270° C.                              3.2   NHCH.sub.3            m.p. 243-247° C.                           3.3   Piperidinyl           m.p. 91,5-93,5° C.                         3.4   Morpholinyl           m.p. 138-141° C.                           3.5   NHCH(CH.sub.3)C.sub.2 H.sub.5                                                                       m.p. 134° C.                               3.6   NHC.sub.6 H.sub.5     m.p. 180-183° C.                           3.7   NHCH.sub.2 COOC.sub.2 H.sub.5                                                                       m.p. 119-122° C.                           3.8   N(CH.sub.3).sub.2     m.p. 83-85° C.                             3.9   NHCH.sub.2 COOH       m.p. 207° C.                               3.10  Pyrrolidinyl                                                            3.11  Q.sub.15              m.p. 150-153° C.                           3.12  Q.sub.47                                                                3.13  N(CH.sub.2 CN).sub.2  m.p. 197-199° C.                           3.14  N(CH.sub.2 CH.sub.2 CN).sub.2                                           3.15  NHCH.sub.2 CH.sub.2 OCH.sub.3                                           3.16  Q.sub.24                                                                3.17  Q.sub.31              m.p. 119-121° C.                           3.18  Q.sub.32                                                                3.19  NHQ.sub.33            m.p. 225-227° C.                           3.20  NHQ.sub.34            decomp. 303° C.                            3.21  NHQ.sub.41                                                              3.22  NHQ.sub.43                                                              3.23  NHQ.sub.44                                                              3.24  NHCH.sub.2 CCH        m.p. 229-231° C.                           3.25  NHCH(CH.sub.3)COOCH.sub.3                                               3.26  N(CH.sub.2 CHCH.sub.2).sub.2                                                                        m.p. 119° C.                               3.27  NH(5-Ethyl-6-chloro-pyrimidin-4-yl)                                                                 m.p. 185-187° C.                           ______________________________________                                        Comp.                                                                         no.   N(R.sub.1)R.sub.2     Physical data                                     ______________________________________                                        3.28                                                                                 ##STR84##            m.p. 140-142° C.                           3.29                                                                                 ##STR85##            m.p. 142-145° C.                           3.30                                                                                 ##STR86##            m.p. 206-206° C.                           3.31  N(CH.sub.3)OCH.sub.3  m.p. 115-117° C.                           3.32  N(CH.sub.3)OCH(CH.sub.3).sub.2                                          3.33  N(C.sub.2 H.sub.5)OCH.sub.3                                             3.34  N(i-C.sub.4 H.sub.9)OCH.sub.3                                           3.35  NHCH.sub.2 CN                                                           3.36  NH-Benzyl             m.p. 148-150° C.                           3.37  NH-4-Chlorobenzyl                                                       3.38  NH-3-Chlorobenzyl                                                       3.39  NH-2-Chlorobenzyl     m.p. 173-175° C.                           3.40  NH-2,4-Dichlorobenzyl m.p. 171-174° C.                           3.41  NH-3,4-Dichlorobenzyl m.p. 185-188° C.                           3.42  NH-2-Fluorobenzyl     m.p. 145-147° C.                           3.43  NH-4-Fluorobenzyl                                                       3.44  NH-2-Methylbenzyl     m.p. 164-165° C.                           3.45  NHCH(Methyl)Q.sub.21  m.p. 127-129° C.                           3.46  2-Methylpiperdine-1-yl                                                                              m.p. 94-96° C.                             3.47  NH-4-Methylpenzyl                                                       3.48  N(Methyl)-benzyl      m.p. 101-103° C.                           3.49  NHCH.sub.2Q.sub.21    m.p. 141-143° C.                           3.50  NHQ.sub.48            m.p. 278-281° C.                           3.51  NHOH                  decomp. >87° C.                            3.52  Q.sub.18                                                                ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR87##                                                                    Comp.                                                                         no.   R.sub.3 '   R.sub.4 '     Physical data                                 ______________________________________                                        4.1   CH.sub.3    CH.sub.3      m.p. 166-168° C.                       4.2   CH.sub.3    C.sub.2 H.sub.5                                                                             m.p. 159-162° C.                       4.3   C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                             4.4   C.sub.3 H.sub.7 -n                                                                        C.sub.3 H.sub.7 -n                                          4.5   C.sub.4 H.sub.9 -n                                                                        C.sub.4 H.sub.9 -n                                          4.6   C.sub.4 H.sub.9 -s                                                                        C.sub.4 H.sub.9 -s                                          4.7   C.sub.6 H.sub.13 -n                                                                       C.sub.6 H.sub.13 -n                                         4.8   CH.sub.2 CH.sub.2 CH.sub.2                                              4.9   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                 m.p. 154-157° C.                           4.10  CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2                                4.11  CH.sub.2 CH.sub. 2 CH.sub.2 CH.sub.2 CH.sub.2CH.sub.2                                               m.p. 134-136° C.                           4.12  H           CH.sub.3                                                    4.13  H           C.sub.2 H.sub.5                                             4.14  H           CHCH.sub.2                                                  4.15  H           C.sub.6 H.sub.5                                                                             m.p. 266-268° C.                       4.16  H           C.sub.6 H.sub.4 Cl(2)                                       4.17  H           C.sub.6 H.sub.4 Cl(4)                                       4.18  CH.sub.3    C.sub.6 H.sub.5                                             4.19  CH.sub.3    C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                              m.p. 209-210° C.                       4.20  H           Q.sub.41      m.p. 226-228° C.                       4.21  H           Q.sub.42                                                    4.22  CH.sub.3    Q.sub.41                                                    4.23  H           Q.sub.21      m.p. 231--232° C.                      4.24  H           CCl.sub.3     m.p. 174-175° C.                       4.25  CH.sub.3    CH.sub.2 OCH.sub.3                                          ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR88##                                                                    Comp.                                                                         no.    R.sub.3 ' R.sub.4 '     Physical data                                  ______________________________________                                        5.1    CH.sub.3  CH.sub.3      m.p. 145-147° C.                        5.2    CH.sub.3  C.sub.2 H.sub.5                                                                             m.p. 148-150° C.                        5.3    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                             m.p. 148-150° C.                        5.4    C.sub.3 H.sub.7 -n                                                                      C.sub.3 H.sub.7 -n                                           5.5    C.sub.4 H.sub.9 -n                                                                      C.sub.4 H.sub.9 -n                                           5.6    C.sub.6 H.sub.13 -n                                                                     C.sub.6 H.sub.13 -n                                          5.7    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                                     5.8    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                                                                m.p. 154-156° C.                            5.9    CH.sub.2 (CH.sub.2).sub.4 CH.sub.2                                                                m.p. 166-168° C.                            5.10   H         CH.sub.3                                                     5.11   H         C.sub. 2 H.sub.5                                             5.12   H         C.sub.6 H.sub.5                                                                             m.p. >166° C.                           5.13   H         o-ClC.sub.6 H.sub.4                                          5.14   CH.sub.3  C.sub.6 H.sub.5                                              5.15   CH.sub.3  2,4-Di-ClC.sub.6 H.sub.3                                     5.16   H         Q.sub.41                                                     5.17   H         Q.sub.42                                                     5.18   CH.sub.3  Q.sub.41                                                     5.19   H         Q.sub.21                                                     5.20   CH.sub.2  CH.sub.2 OCH.sub.3                                           5.21   CH.sub.3  CH.sub.2 CH.sub.2 OCH.sub.3                                  5.22   H         Q.sub.24                                                     ______________________________________                                    

                                      TABLE 6                                     __________________________________________________________________________     ##STR89##                                                                    Comp.                                                                         no.  R.sub.5                                                                             R.sub.4   R.sub.3   Physical data                                  __________________________________________________________________________    6.1  H     H         H         m.p. 270-272° C.                        6.2  H     CH.sub.3  H                                                        6.3  H     COCH.sub.3                                                                              H                                                        6.4  H     COC.sub.2 H.sub.5                                                                       H                                                        6.5  H     COCHCH.sub.2                                                                            H                                                        6.6  H                                                                                    ##STR90##                                                                              H                                                        6.7  COCH.sub.3                                                                          COCH.sub.3                                                                              H                                                        6.8  H     H         C.sub.6 H.sub.5                                          6.9  H     H         Q.sub.41                                                 6.10 H     COCH.sub.3                                                                              Q.sub.21                                                 6.11 H     H         Q.sub.34                                                 6.12 CH.sub.3                                                                            COCH.sub.3                                                                              Q.sub.41                                                 6.13 H     COCH.sub.3                                                                              Q.sub.41                                                 6.14 H     COCH.sub.2 OCH.sub.3                                                                    H                                                        6.15 H     COCH.sub.2 OCH.sub.3                                                                    Q.sub.41                                                 6.16 H                                                                                    ##STR91##                                                                              Q.sub.41                                                 6.17 COCH.sub.3                                                                          COCH.sub.3                                                                              Q.sub.41                                                 6.18 H     H         Q.sub.43                                                 6.19 H     COCH.sub.3                                                                              Q.sub.44                                                 6.20 H     COCH.sub.3                                                                              Q.sub.43                                                 6.21 H     H         Q.sub.44                                                 6.22 H     H         Q.sub.21                                                 6.23 H     sec-Butyl sec-Butyl m.p. 92-95° C.                          6.24 H     COCH.sub.3                                                                              sec-Butyl m.p. 100-102° C.                        6.25 H     CH.sub.3  CH.sub.3                                                 6.26 H     CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                          CH(CH.sub.3)CH.sub.2 OCH.sub.3                           6.27 H     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                          6.28 CH.sub.3                                                                            sec-Butyl sec-Butyl                                                6.29 H     COCH.sub.3                                                                              CH.sub.3                                                 6.30 H     COCH.sub.3                                                                              CH.sub.2 OCH.sub.3                                       6.31 H     COCH.sub.3                                                                              C.sub.2 H.sub.5                                          6.32 H     COC.sub.2 H.sub.5                                                                       sec-Butyl                                                6.33 H     COCH.sub.2 OCH.sub.3                                                                    sec-Butyl                                                6.34 H     COCH.sub.2 OCH.sub.3                                                                    C.sub.2 H.sub.5                                          6.35 H     COCH.sub.3                                                                              n-Propyl                                                 6.36 H     COCH.sub.3                                                                              i-Propyl                                                 6.37 H     n-Propyl  n-Propyl                                                 6.38 H     i-Propyl  i-Propyl  m.p. 173-175° C.                        __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________     ##STR92##                                                                    Comp.                                                                         no. Y    X     Z              Physical data                                   __________________________________________________________________________    7.1 Br   H     COOCH.sub.3    m.p. 138-141° C.                         7.2 Cl   H     COOCH.sub.3    m.p. 142° C.                             7.3 Cl   H     COOH                                                           7.4 H    6-Cl  COOCH.sub.3    m.p. 111-114° C.                         7.5 H    6-Cl  COOH           m.p. 255-260° C.                         7.6 H    6-F   COOCH.sub.3    m.p. 122-125° C.                         7.7 Br   H     COOH                                                           7.8 H    6-F   COOH                                                           7.9 H    6-F   COOC.sub.2 H.sub.5                                             7.10                                                                              H    6-F   COOC.sub.3 H.sub.7 (n)                                         7.11                                                                              H    6-F   COOCH(CH.sub.3)COOC.sub.2 H.sub.5                              7.12                                                                              Cl   H     CN                                                             7.13                                                                              H    4-Br  CN                                                             7.14                                                                              H    4-Cl  CN                                                             7.15                                                                              H    6-F   CN                                                             7.16                                                                              F    H     CN                                                             7.17                                                                              H    4-F   CN                                                             7.18                                                                              H    4-COOH                                                                              COOH                                                           7.19                                                                              H    4-COOCH.sub.3                                                                       COOCH.sub.3                                                    7.20                                                                              H    6-OH  COOH                                                           7.21                                                                              H    6-OH  COOCH.sub.3                                                    7.22                                                                              H    6-OCH.sub.3                                                                         COOCH.sub.3                                                    7.23                                                                              H    4-CH.sub.3                                                                          COOCH.sub.3                                                    7.24                                                                              F    4-F   COOCH.sub.3                                                    7.25                                                                              F    6-F   COOCH.sub.3                                                    7.26                                                                              H    H     CN             m.p. 116-118° C.                         7.27                                                                              SO.sub.3 H                                                                         H     CN                                                             7.28                                                                              SO.sub.3 H                                                                         H     COOH                                                           7.29                                                                              SO.sub.3 H                                                                         H     COOCH.sub.3                                                    7.30                                                                              NO.sub.2                                                                           H     COOH                                                           7.31                                                                              NO.sub.2                                                                           H     COOCH.sub.3                                                    7.32                                                                              SO.sub.3 Na                                                                        H     COONa                                                          7.33                                                                              SO.sub.3 Na                                                                        H     CN                                                             7.34                                                                              NH.sub.2                                                                           H     CN                                                             7.35                                                                              NH.sub.2                                                                           H     COOH                                                           7.36                                                                              NH.sub.2                                                                           H     COOCH.sub.3                                                    7.37                                                                              SO.sub.3 H                                                                         6-F   COOCH.sub.3                                                    7.38                                                                              H    6-F   CONHOH                                                         7.39                                                                              H    6-F   CONHNH.sub.2                                                   7.40                                                                              H    6-Cl  CONHNH.sub.2   decomp. 240° C.                          7.41                                                                              H    6-Cl                                                                                 ##STR93##                                                     7.42                                                                              H    6-F   COOCH.sub.2Q.sub.21                                            7.43                                                                              H    6-Cl  CONHQ.sub.34                                                   7.44                                                                              H    6-COOH                                                                              COOH                                                           7.45                                                                              H    6-Cl                                                                                 ##STR94##                                                     7.46                                                                              H    6-Cl                                                                                 ##STR95##                                                     7.47                                                                              F    H                                                                                    ##STR96##                                                     7.48                                                                              F    H     COOQ.sub.46                                                    7.49                                                                              H    6-Cl  COOCH.sub.2Q.sub.32                                            7.50                                                                              NO.sub.2                                                                           H     COQ.sub.16                                                     7.51                                                                              H    6-Cl  CN                                                             7.52                                                                              F    H     COO-benzyl                                                     7.53                                                                              H    6-F   COO-benzyl                                                     7.54                                                                              H    4-F   COO-benzyl                                                     7.55                                                                              NH.sub.2                                                                           H     COO-benzyl                                                     7.56                                                                              NO.sub.2                                                                           H     COO-benzyl                                                     7.57                                                                              OH   H     COOCH.sub.3                                                    7.58                                                                              F    H     CONH.sub.2                                                     7.59                                                                              F    H     COOH                                                           7.60                                                                              F    H     COOCH.sub.3                                                    7.61                                                                              F    H     COOC.sub.2 H.sub.5                                                                           m.p. 68-69° C.                           7.62                                                                              F    H     COOCH.sub.2 CH.sub.2 CH.sub.3                                  7.63                                                                              F    H     COOCH(CH.sub.3).sub.2                                          7.64                                                                              F    H     COOCH.sub.2 C.sub.6 H.sub.4 -o-Cl                              7.65                                                                              F    H     COOCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3                        7.66                                                                              F    H     CON(OCH.sub.3)CH.sub.3                                         __________________________________________________________________________

                  TABLE 8                                                         ______________________________________                                         ##STR97##                                                                    Comp.                                                                         no.   Y*    X*     Z*               Physical data                             ______________________________________                                        8.1   H     H      COCl             m.p. 107° C.                       8.2   H     H      COBr                                                       8.3   H     H      COF                                                        8.4   H     H      COJ                                                        8.5   H     H      COOCOCH.sub.3                                              8.6   H     H                                                                                     ##STR98##       m.p. 117-119° C.                   8.7   H     H      COOCO -Phenyl                                              8.8   F     6-F    COCl                                                       8.9   H     6-F    COCl                                                       8.10  F     H      COCl                                                       8.11  H     6-F                                                                                   ##STR99##                                                 8.12  F     H                                                                                     ##STR100##                                                8.13  H     H      COOSO.sub.2CH.sub.3                                        8.14  H     H      COOOSO.sub.2 -Phenyl                                       ______________________________________                                    

In Table 9 below intermediate compounds are exemplified which constitutepart of this invention.

                                      TABLE 9                                     __________________________________________________________________________     ##STR101##                                                                   Comp.                            Physical                                     no. X Y  Z         E             data                                         __________________________________________________________________________    9.1 H NH.sub.2                                                                         COOH      CH.sub.2 C.sub.6 H.sub.5                                                                    m.p. 124-125° C.                      9.2 H NH.sub.2                                                                         COOCH.sub.3                                                                             CH.sub.2 C.sub.6 H.sub.5                                                                    m.p. 84-86° C.                        9.3 H NH.sub.2                                                                         COOC.sub.2 H.sub.5                                                                      CH.sub.2 C.sub.6 H.sub.5                                   9.4 H NH.sub.2                                                                         COOCH(CH.sub.3).sub.2                                                                   CH.sub.2 C.sub.6 H.sub.5                                   9.5 H NH.sub.2                                                                         COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH.sub.2 C.sub.6 H.sub.5                                   9.6 H NH.sub.2                                                                         COO(CH.sub.2).sub.3 CH.sub.3                                                            CH.sub.2 C.sub.6 H.sub.5                                   9.7 H NH.sub.2                                                                         COOCH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.8 H H  COOH      CH.sub.2 C.sub.6 H.sub.5                                                                    m.p. 98° C.                           9.9 H H  COOCH.sub.3                                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.10                                                                              H H  COOC.sub.2 H.sub.5                                                                      CH.sub.2 C.sub.6 H.sub.5                                   9.11                                                                              H H  COOCH(CH.sub.3).sub.2                                                                   CH.sub.2 C.sub.6 H.sub.5                                   9.12                                                                              H H  COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH.sub.2 C.sub.6 H.sub.5                                   9.13                                                                              H H  COO(CH.sub.2).sub.3 CH.sub.3                                                            CH.sub.2 C.sub.6 H.sub.5                                   9.14                                                                              H H  COOCH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.15                                                                              H NH.sub.2                                                                         COOH      CH(CH.sub.3).sub.2                                         9.16                                                                              H NH.sub.2                                                                         COOCH.sub.3                                                                             CH(CH.sub.3).sub.2                                                                          m.p. 109-110° C.                      9.17                                                                              H NH.sub.2                                                                         COOC.sub.2 H.sub.5                                                                      CH(CH.sub.3).sub.2                                         9.18                                                                              H NH.sub.2                                                                         COOCH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                         9.19                                                                              H NH.sub.2                                                                         COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH(CH.sub.3).sub.2                                         9.20                                                                              H NH.sub.2                                                                         COO(CH.sub.2).sub.3 CH.sub.3                                                            CH(CH.sub.3).sub.2                                         9.21                                                                              H NH.sub.2                                                                         COOCH.sub.2 C.sub.6 H.sub.5                                                             CH(CH.sub.3).sub.2                                         9.22                                                                              H NH.sub.2                                                                         COOH      H                                                          9.23                                                                              H NH.sub.2                                                                         COOCH.sub.3                                                                             H                                                          9.24                                                                              H NH.sub.2                                                                         COOC.sub.2 H.sub.5                                                                      H                                                          9.25                                                                              H NH.sub.2                                                                         COOCH(CH.sub.3).sub.2                                                                   H                                                          9.26                                                                              H NH.sub.2                                                                         COOCH.sub.2 CH.sub.2 CH.sub.3                                                           H                                                          9.27                                                                              H NH.sub.2                                                                         COOCH.sub.2 C.sub.6 H.sub.5                                                             H                                                          9.28                                                                              H H  COOH      CH(CH.sub.3).sub.2                                         9.29                                                                              H H  COOCH.sub.3                                                                             CH(CH.sub.3).sub.2                                         9.30                                                                              H H  COOC.sub.2 H.sub.5                                                                      CH(CH.sub.3).sub.2                                         9.31                                                                              H H  COOCH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                         9.32                                                                              H H  COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH(CH.sub.3).sub.2                                         9.33                                                                              H H  COOCH.sub.2 C.sub.6 H.sub.5                                                             CH(CH.sub.3).sub.2                                         9.34                                                                              H Br COOH      CH.sub.2 C.sub.6 H.sub.5                                   9.35                                                                              H Br COCH.sub.3                                                                              CH.sub.2 C.sub.6 H.sub.5                                   9.36                                                                              H Br COOC.sub.2 H.sub.5                                                                      CH.sub.2 C.sub.6 H.sub.5                                   9.37                                                                              H Br COOCH(CH.sub.3).sub.2                                                                   CH.sub.2 C.sub.6 H.sub.5                                   9.38                                                                              H Br COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH.sub.2 C.sub.6 H.sub.5                                   9.39                                                                              H Br COOCH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.40                                                                              H Cl COOH      CH.sub.2 C.sub.6 H.sub.5                                   9.41                                                                              H Cl COOCH.sub.3                                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.42                                                                              H Cl COOC.sub.2 H.sub.5                                                                      CH.sub.2 C.sub.6 H.sub.5                                   9.43                                                                              H Cl COOCH(CH.sub.3).sub.2                                                                   CH.sub.2 C.sub. 6 H.sub.5                                  9.44                                                                              H Cl COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH.sub.2 C.sub.6 H.sub.5                                   9.45                                                                              H Cl COOCH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.46                                                                              Cl                                                                              H  COOCH.sub.3                                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.47                                                                              Cl                                                                              H  COOH      CH.sub.2 C.sub.6 H.sub.5                                   9.48                                                                              F H  COOH      CH.sub.2 C.sub.6 H.sub.5                                   9.49                                                                              F H  COOCH.sub.3                                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.50                                                                              F H  COOC.sub.2 H.sub.5                                                                      CH.sub.2 C.sub.6 H.sub.5                                   9.51                                                                              F H  COOCH(CH.sub.3).sub.2                                                                   CH.sub.2 C.sub.6 H.sub.5                                   9.52                                                                              F H  COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH.sub.2 C.sub.6 H.sub.5                                   9.53                                                                              F H  COOCH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.2 C.sub.6 H.sub.5                                   9.54                                                                              F H  COOCH.sub.3                                                                             CH(CH.sub.3).sub.2                                         9.55                                                                              F H  COOC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                            9.56                                                                              F H  COOCH.sub.3                                                                             CH.sub.3                                                   9.57                                                                              H NH.sub.2                                                                         COOH      CH.sub.3                                                   9.58                                                                              H NH.sub.2                                                                         COOCH.sub.3                                                                             CH.sub.3      m.p. 102-104° C.                      9.59                                                                              H NH.sub.2                                                                         COOC.sub.2 H.sub.5                                                                      CH.sub.3                                                   9.60                                                                              H NH.sub.2                                                                         COOCH(CH.sub.3).sub.2                                                                   CH.sub.3                                                   9.61                                                                              H NH.sub.2                                                                         COOCH.sub.2 CH.sub.2 CH.sub.3                                                           CH.sub.3                                                   9.62                                                                              H NH.sub.2                                                                         COOCHC.sub.6 H.sub.5                                                                    CH.sub.3                                                   9.63                                                                              H NH.sub.2                                                                         COOH      C.sub.2 H.sub.5                                            9.64                                                                              H NH.sub.2                                                                         COOCH.sub.3                                                                             C.sub.2 H.sub.5                                            9.65                                                                              H NH.sub.2                                                                         COOC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                             oil                                          9.66                                                                              H NH.sub.2                                                                         COOCH(CH.sub.3).sub.2                                                                   C.sub.2 H.sub.5                                            9.67                                                                              H NH.sub.2                                                                         COOCH.sub.2 CH.sub.2 CH.sub.3                                                           C.sub.2 H.sub.5                                            9.68                                                                              H NH.sub.2                                                                         COOCH.sub.2 C.sub.6 H.sub.5                                                             C.sub.2 H.sub.5                                            9.69                                                                              H NH.sub.2                                                                         COOCH.sub.3                                                                              ##STR102##                                                9.70                                                                              H NH.sub.2                                                                         COOCH.sub.2 C.sub.6 H.sub.5                                                              ##STR103##                                                9.71                                                                              H NH.sub.2                                                                         COO(CH.sub.2).sub.2 CH.sub.3                                                             ##STR104##                                                9.72                                                                              H NH.sub.2                                                                         COOCH.sub.3                                                                             CH.sub.3 (CH.sub.2).sub.11                                 9.73                                                                              H NH.sub.2                                                                         COOCH.sub.2 C.sub.6 H.sub.5                                                             CH.sub.3 (CH.sub.2).sub.11                                 __________________________________________________________________________

2. FORMULATION EXAMPLES FOR LIQUID ACTIVE INGREDIENTS OF FORMULA I(THROUGHOUT, PERCENTAGES ARE BY WEIGHT)

    ______________________________________                                        2.1. Emulsifiable concentrates                                                                   a)        b)     c)                                        ______________________________________                                        compound of Tables 1 to 8                                                                        25%       40%    50%                                       calcium dodecylbenzenesulfonate                                                                   5%        8%     6%                                       castor oil polyethylene glycol                                                                    5%       --     --                                        ether (36 moles of ethylene oxide)                                            tributylphenol polyethylene glycol                                                               --        12%     4%                                       ether (30 moles of ethylene oxide)                                            cyclohexanone      --        15%    20%                                       xylene mixture     65%       25%    20%                                       ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        2.2. Solutions    a)     b)      c)    d)                                     ______________________________________                                        compound of Tables 1 to 8                                                                       80%    10%     5%    95%                                    ethylene glycol monomethyl                                                                      20%    --      --    --                                     ether                                                                         polyethylene glycol                                                                             --     70%     --    --                                     (mol. wt. 400)                                                                N-methyl-2-pyrrolidone                                                                          --     20%     --    --                                     epoxidised coconut oil                                                                          --     --      1%     5%                                    petroleum fraction (boiling range                                                               --     --      94%   --                                     160-190° C.)                                                           ______________________________________                                    

These solutions are suitable for application in the form of micro-drops.

    ______________________________________                                        2.3. Granulates      a)      b)                                               ______________________________________                                        compound of Tables 1 to 8                                                                          5%      10%                                              kaolin               94%     --                                               highly dispersed silicic acid                                                                      1%      --                                               attapulgite          --      90%                                              ______________________________________                                    

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo.

    ______________________________________                                        2.4. Dusts          a)      b)                                                ______________________________________                                        compound of Tables 1 to 8                                                                         2%      5%                                                highly dispersed silicic acid                                                                     1%      5%                                                talcum              97%     --                                                kaolin              --      90%                                               ______________________________________                                    

Ready-for-use dusts are obtained by intimately mixing the carriers withthe active ingredient.

FORMULATION EXAMPLES FOR SOLID ACTIVE INGREDIENTS OF FORMULA I(THROUGHOUT, PERCENTAGES ARE BY WEIGHT)

    ______________________________________                                        2.5. Wettable powders                                                                            a)        b)     c)                                        ______________________________________                                        compound of Tables 1 to 8                                                                        25%       50%    75%                                       sodium lignosulfonate                                                                            5%         5%    --                                        sodium lauryl sulfate                                                                            3%        --      5%                                       sodium diisobutylnaphthalene-                                                                    --         6%    10%                                       sulfonate                                                                     octylphenol polyethylene glycol                                               ether (7-8 moles of ethylene oxide)                                                              --         2%    --                                        highly dispersed silicic acid                                                                    5%        10%    10%                                       kaolin             62%       27%    --                                        ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is ground homogeneously in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        2.6. Emulsifiable concentrate                                                 ______________________________________                                        compound of Tables 1 to 8                                                                            10%                                                    octylphenol polyethylene glycol                                                                       3%                                                    ether (4-5 moles of ethylene oxide)                                           calcium dodecylbenzenesulfonate                                                                       3%                                                    castor oil polyglycol ether                                                                           4%                                                    (35 moles of ethylene oxide)                                                  cyclohexanone          30%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        2.7. Dusts           a)     b)                                                ______________________________________                                        compound of Tables 1 to 8                                                                           5%     8%                                               talcum               95%    --                                                kaolin               --     92%                                               ______________________________________                                    

Ready-for-use dusts are obtained by mixing the active ingredient withthe carriers and grinding the mixture in a suitable mill.

    ______________________________________                                        2.8. Extruder granulate                                                       ______________________________________                                        compound of Tables 1 to 8                                                                         10%                                                       sodium lignosulfonate                                                                              2%                                                       carboxymethylcellulose                                                                             1%                                                       kaolin              87%                                                       ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        2.9. Coated granulate                                                         ______________________________________                                        compound of Tables 1 to 8                                                                           3%                                                      polyethylene glycol (mol. wt. 200)                                                                  3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        2.10. Suspension concentrate                                                  ______________________________________                                        compound of Tables 1 to 8                                                                           40%                                                     ethylene glycol       10%                                                     nonylphenol polyethylene glycol                                                                      6%                                                     ether (15 moles of ethylene oxide                                             sodium lignosulfonate 10%                                                     carboxymethylcellulose                                                                               1%                                                     37% aqueous formaldehyde solution                                                                    0.2%                                                   silicone oil in the form of a 75%                                                                    0.8%                                                   aqueous emulsion                                                              water                 32%                                                     ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

3. BIOLOGICAL EXAMPLES Example 3.1 Immunising action againstColletotrichum lagenarium on Cucumis sativus L.

A) Foliar application

After a cultivation period of 2 weeks, cucumber plants are sprayed witha spray mixture (concentration: 0.02% active ingredient) prepared from awettable powder formulation of the test compound.

After one week the plants are infected with a spore suspension (1.5×10⁵spores/ml) of the fungus and incubated in the dark for 36 hours at highhumidity and at a temperature of 23° C. Incubation is then continued atnormal humidity and 22° to 23° C.

Evaluation of the protective action is made 7 to 8 days after infectionand is based on the fungus attack.

B) Soil application

After a cultivation period of 2 weeks, cucumber plants are treated bysoil application with a spray mixture (concentration: 0.002% activeingredient, based on the volume of the soil) prepared from a wettablepowder formulation of the test compound.

One week later the plants are infected with a spore suspension (1.5×10⁵spores/ml) of the fungus and incubated in the dark for 36 hours at highhumidity and at a temperature of 23° C. Incubation is then continued atnormal humidity and 22°-23° C.

Evaluation of the protective action is made 7 to 8 days after infectionand is based on the fungus attack.

C) Dressing

Cucumber seeds are dressed with a solution of the test compound(concentration: 180 g of active ingredient/100 kg of seed). The seedsare sown. After 4 weeks the plants are infected with a spore suspension(1.5×10⁵ spores/ml) of the fungus and incubated for 36 hours at highhumidity and at a temperature of 23° C. Incubation is then continued atnormal humidity and 22° to 23° C. Evaluation of the protective action ismade 7 to 8 days after infection and is based on the fungus attack.

Untreated and infected control plants in tests A and B and infectedplants the seeds of which have not been treated in test C exhibit 100%fungus attack.

Compounds of Tables 1 to 7 result in good immunisation againstColletotrichum lagenarium. Thus, plants treated e.g. with compound no.1.1, 1.2, 1.3, 1.4, 1.5, 1.34, 1.39, 1.46, 1.79, 1.81, 1.86, 1.101,1.116, 1.136, 1.139, 1.140, 1.144, 2.5, 3.29, 7.6 or 7.26 remainvirtually completely free of Colletotrichum (20 to 0% attack).

Example 3.2 Comparison test: direct action against Colletotrichumlagenarium

The formulated test compound is mixed at various concentrations (100,10, 1, 0.1 ppm) with nutrient substrate (vegetable juice) which has beenautoclaved and cooled and which contains 10³ spores/ml, and the mixtureis poured onto microtiter plates. The plates are then incubated in thedark at 22° C. After 2-3 days the growth of the fungus is measured byspectrophotometry and the EC₅₀ values are determined.

In the case of e.g. compound 1.1, 1.2, 1.4, 1.34, 1.39, 1.79, 1.81,1.86, 1.100, 1.101, 1.116, 1.135, 1.136, 1.139, 1.140, 1.144, 2.5, 3.26,3.29 or 7.6, no inhibition of the growth of the fungus is observed. Incontrast, when the fungicide benomyl (commercially available product)##STR105## is used as comparison substance at 0.2 ppm, a 50% inhibition(EC₅₀) of Colletotrichum lagenarium occurs.

Example 3.3 Immunising action against Pyricularia oryzae on rice plants

A) Foliar application

After a cultivation period of 3 weeks, rice plants are treated by foliarapplication with a spray mixture (concentration: 0.02% activeingredient) prepared from a wettable powder formulation of the testcompound. After 2-3 days the plants are inoculated with a sporesuspension (350,000 spores/ml) and incubated for 7 days at high humidityand at a temperature of 24° C. Evaluation of the protective action ismade 7-8 days after inoculation and is based on the fungus attack.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 8 result in good immunisation againstPyricularia oryzae. Thus, plants treated e.g. with compound 1.2, 1.34,1.37, 1.38, 1.39, 1.72, 1.79, 1.86, 1.96, 1.103, 1.119, 1.135, 2.2, 2.3,3.1, 3.2, 3.8, 3.9, 3.13, 4.2, 5.2 or 7.2 remain virtually completelyfree of Pyricularia oryzae (20 to 0% attack).

B) Soil application

After a cultivation period of 3 weeks, rice plants are treated by soilapplication with a spray mixture (concentration: 0.002% activeingredient, based on the volume of the soil) prepared from a wettablepowder formulation of the test compound. After 2-3 days the plants areinoculated with a spore suspension (35×10⁵ spores/ml) and incubated for7 days at high humidity and at a temperature of 24° C.

Evaluation of the protective action is made 7 to 8 days afterinoculation and is based on the fungus attack.

Untreated and infected control plants exhibit 100% attack in this test.Compounds of Tables 1 to 7 exhibit good activity against Pyriculariaoryzae. Thus, plants treated e.g. with compounds 1.2, 1.34, 1.37, 1.38,1.39, 1.79, 1.96, 1.103, 1.119, 1.135, 2.2, 2.3, 3.1, 3.9, 3.13 or 7.3remain virtually completely free of Pyricularia oryzae (20 to 0%attack).

Example 3.4 Comparison test: direct action against Pyricularia oryzae

The formulated test compound is mixed at various concentrations (100,10, 1, 0.1 ppm) with nutrient substrate (vegetable juice) which has beenautoclaved and cooled and which contains 10³ spores/ml, and the mixtureis poured onto microtiter plates. The plates are incubated in the darkat 22° C. After 2-3 days the growth of the fungus is determined byspectrophotometry.

In the case of e.g. compound 1.1, 1.2, 1.3, 1.4, 1.5, 1.34, 1.37, 1.39,1.72, 1.86, 1.96, 1.100, 1.101, 1.103, 1.108, 1.140, 2.5, 3.1, 3.9,3.26, 7.26 or 7.6, no inhibition of the growth of the fungus isobserved. In contrast, when the fungicide benomyl (commerciallyavailable product/see Example 3.2) is used as comparison substance at0.1 ppm, a 50% inhibition (EC₅₀) of Pyricularia oryzae occurs.

Example 3.5 Immunising action against Pseudomonas lachrymans on Cucumissativus L.

A) Foliar application

After a cultivation period of 2 weeks, cucumber plants are sprayed witha spray mixture (concentration: 0.02% active ingredient) prepared from awettable powder formulation of the test compound.

After one week the plants are infected with a bacteria suspension (10⁸bacteria/ml) and incubated for 7 days at high humidity and at atemperature of 23° C.

Evaluation of the protective action is made 7 to 8 days after infectionand is based on the bacteria attack.

Compounds of Tables 1 to 7 result in good immunisation againstPseudomonas lachrymans. Thus, plants treated e.g. with compound 1.2,1.3, 1.4, 1.5, 1.9, 1.34, 1.38, 1.46, 1.72, 1.79, 1.81, 1.119, 1.135,2.2, 2.3, 3.1, 3.28, 3.29 or 7.26 remain substantially free ofPseudomonas (20 to 0% attack).

B) Soil application

After a cultivation period of 2 weeks, cucumber plants are treated bysoil application with a spray mixture (concentration: 0.002% activeingredient, based on the volume of the soil) prepared from a wettablepowder formulation of the test compound.

After one week the plants are infected with a bacteria suspension (10⁸bacteria/ml) and incubated for 7 days at high humidity and at atemperature of 23° C.

Evaluation of the protective action is made 7 to 8 days after infectionand is based on the bacteria attack.

Compounds of Tables 1 to 7 result in good immunisation againstPseudomonas lachrymans. Thus, plants treated e.g. with compound 1.1,1.2, 1.3, 1.4, 1.5, 1.9, 1.34, 1.38, 1.46, 1.72, 1.79, 1.81, 1.119,1.135, 2.2, 2.3, 3.1, 3.9, 3.28, 3.29 or 7.26 remain virtuallycompletely free of Pseudomonas (20 to 0% attack).

Untreated and infected control plants exhibit 100% attack of the diseasein tests A and B.

Example 3.6 Comparison test: direct action against Pseudomonaslachrymans

The formulated test compound is mixed at various concentrations (100,10, 1, 0.1 ppm) with nutrient broth (0.8%) which has been autoclaved andcooled and which contains 10⁶ bacteria/ml, and the mixture is pouredonto microtiter plates. The plates are then incubated in the dark at 22°C. on a vibrator table (120 rpm). After an incubation period of 2-3 daysthe growth of the bacteria is determined by spectrophotometry.

In the case of e.g. compound 1.1, 1.2, 1.3, 1.4, 1.5, 1.34, 1.38, 1.72,1.79, 1.81, 1.96, 1.101, 1.119, 1.140, 2.2, 2.3, 2.5, 3.1, 3.6, 3.9,3.26, 3.28, 3.29 or 7.26, no inhibition of the growth of the bacteria isobserved. In contrast, when the bactericide streptomycin is used ascomparison substance at 0.4 ppm, a 50% inhibition (EC₅₀) of Pseudomonaslachrymans occurs.

Example 3.7 Immunising action against Xanthomonas oryzae on rice plants

A) Foliar application

After a cultivation period of 3 weeks, rice plants are treated by foliarapplication with a spray mixture (concentration: 0.02% activeingredient) prepared from a wettable powder formulation of the testcompound. After 2-3 days the plants are inoculated with a bacteriasuspension (10⁸ bacteria/ml) and incubated for 7 days at high humidityand at a temperature of 24° C. Evaluation of the protective action ismade 7-8 days after inoculation and is based on the bacteria attack.

Compounds of the Tables result in good immunisation against Xanthomonasoryzae. Thus, plants treated e.g. with compound 1.3, 1.5, 1.16, 1.37,1.38, 1.72, 1.81, 1.86, 1.95, 1.102, 1.103, 1.108, 1.136, 1.139, 2.2,2.5 or 3.29 remain virtually completely free of Xanthomonas oryzae (20to 0% attack).

B) Soil application

After a cultivation period of 3 weeks, rice plants are treated by soilapplication with a spray mixture (concentration: 0.002% activeingredient, based on the volume of the soil) prepared from a wettablepowder formulation of the test compound. After 2-3 days the plants areinoculated with a bacteria suspension (10⁸ bacteria/ml) and incubatedfor 7 days at high humidity and at a temperature of 24° C.

Evaluation of the protective action is made 7-8 days after inoculationand is based on the bacteria attack.

Compounds of Tables 1 to 7 result in good immunisation againstXanthomonas oryzae. Thus, plants treated e.g. with compound 1.2, 1.3,1.4, 1.5, 1.6, 1.9, 1.16, 1.34, 1.35, 1.38, 1.44, 1.46, 1.68, 1.71,1.72, 1.81, 1.86, 1.96, 1.102, 1.103, 1.119, 1.135, 1.136, 2.2, 2.3,2.5, 3.1, 3.13, 3.28, 3.29, 7.2, 7.5 or 7.26 remain virtually completelyfree of Xanthomonas oryzae (20 to 0% attack).

Untreated and infected control plants exhibit 100% attack in tests A andB.

Example 3.8 Comparison test: direct action against Xanthomonas oryzae

The formulated test compound is mixed at various concentrations (100,10, 1, 0.1 ppm) with nutrient broth (0.8%) which has been autoclaved andcooled and which contains 10⁶ bacteria/ml, and the mixture is pouredonto microtiter plates. The plates are incubated in the dark at 22° C.on a vibrator table (120 rpm). After 2-3 days the growth of the bacteriais determined by spectrophotometry.

In the case of e.g. compound 1.1, 1.2, 1.3, 1.4, 1.5, 1.9, 1.34, 1.38,1.81, 1.101, 1.119, 1.135, 1.140, 2.3 or 2.5, no inhibition of thegrowth of the bacteria is observed. In contrast, when the bactericidestreptomycin is used as comparison substance at 0.4 ppm, a 50%inhibition (EC₅₀) of Xanthomonas oryzae occurs.

Example 3.9 Immunising action against Xanthomonas vesicatoria on paprikaplants

A) Foliar application

After a cultivation period of 4 weeks, paprika plants are treated byfoliar application with a spray mixture (concentration: 0.02% activeingredient) prepared from a wettable powder formulation of the testcompound. After 2-3 days the plants are inoculated with a bacteriasuspension (10⁸ bacteria/ml) and incubated for 6 days at high humidityand at a temperature of 25° C. Evaluation of the protective action ismade 7-8 days after inoculation and is based on the bacteria attack.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 7 result in good immunisation againstXanthomonas vesicatoria. Thus, plants treated e.g. with compound 1.2,1.5, 1.9, 1.16, 1.34, 1.35, 1.37, 1.72, 1.81, 1.86, 1.96, 1.102, 1.103,1.108, 1.136, 3.1, 3.13, 3.28, 3.29, 5.2, 7.26 or 7.5 remain virtuallycompletely free of Xanthomonas vesicatoria (20 to 0% attack).

B) Soil application

After a cultivation period of 4 weeks, paprika plants are treated bysoil application with a spray mixture (concentration: 60 ppm, based onthe volume of the soil) prepared from a wettable powder formulation ofthe test compound. After 2-3 days the plants are inoculated with abacteria suspension (10⁸ bacteria/ml) and incubated for 6 days at highhumidity and at a temperature of 25° C.

Evaluation of the protective action is made 7-8 days after inoculationand is based on the bacteria attack.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 7 result in good immunisation againstXanthomonas vesicatoria. Thus, plants treated e.g. with compound 1.2,1.5, 1.6, 1.9, 1.11, 1.16, 1.34, 1.35, 1.36, 1.37, 1.39, 1.68, 1.71,1.72, 1.81, 1.86, 1.95, 1.100, 1.102, 1.103, 1.108, 1.116, 1.140, 1.144,2.5, 3.1, 3.13, 3.28, 3.29, 5.2, 7.2 or 7.26 remain virtually completelyfree of Xanthomonas vesicatoria (20 to 0% attack).

Example 3.10 Immunising action against Phytophthora infestans on tomatoplants

A) Foliar application

After a cultivation period of 3 weeks, tomato plants are sprayed with aspray mixture (0.02% active ingredient) prepared from a wettable powderformulation of the test compound. After 2-3 days the treated plants areinfected with a sporangia suspension of the fungus (5×10⁴ sporangia/ml).Evaluation of the protective action is made after incubation of theinfected plants for 5 days at 90-100% relative humidity and 20° C.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 7 result in good immunisation againstPhytophthora infestans. Thus, plants treated e.g. with compound 1.6,1.16, 1.34, 1.44, 1.68, 1.71, 1.72, 1.96, 1.101, 3.9 or 7.26 remainsubstantially free of Phytophthora (20 to 0% attack).

B) Soil application

After a cultivation period of 3 weeks, a spray mixture (0.006% activeingredient, based on the volume of the soil) prepared from a wettablepowder formulation of the test compound is poured onto tomato plants.Care is taken that the spray mixture does not come into contact with theparts of the plants above the soil. After 4 days the treated plants areinfected with a sporangia suspension (5×10⁴ sporangia/ml) of the fungus.Evaluation of the protective action is made after incubation of theinfected plants for 5 days at 90-100% relative humidity and 20° C.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 7 result in good immunisation againstPhytophthora infestans. Thus, plants treated e.g. with compound 1.6,1.34, 1.44, 1.68, 1.71, 1.72, 1.101, 3.2, 3.4, 3.6, 3.8, 3.9, 3.13 or7.26 remain substantially free of Phytophthora (20 to 0% attack).

Example 3.11 Comparison test: direct action against Phytophthorainfestans

The formulated test compound is mixed at various concentrations (100,10, 1, 0.1 ppm) with nutrient substrate (peas/agar) which has beensterile-filtered and contains 10⁶ sporangia/ml, and the mixture ispoured onto microtiter plates. The plates are incubated in the dark at22° C. After 2-3 days the growth of the fungus is determined byspectrophotometry.

In the case of e.g. compound 1.1, 1.2, 1.4, 1.34, 1.72, 1.86, 1.104,1.108, 1.116, 1.135, 1.140, 1.144, 2.5, 3.1, 3.6, 3.9, 3.13, 3.26, 7.6or 7.26, no inhibition of the growth of the fungus is observed. Incontrast, when ridomil (commercially available product) is used ascomparison substance at 0.2 ppm, a 50% inhibition of Phytophthorainfestans occurs.

Example 3.12 Immunising action against Plasmopara viticola on vines

Vine seedlings in the 4- to 5-leaf stage are sprayed with a spraymixture (0.02% active ingredient) prepared from a wettable powderformulation of the test compound. After one week the treated plants areinfected with a sporangia suspension (5×10⁴ sporangia/ml) of the fungus.Evaluation of the protective action is made after incubation for 6 daysat 95-100% relative humidity and 20° C.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 8 result in good immunisation againstPlasmopara viticola. Thus, vines treated e.g. with compound 1.1, 1.2 or1.5 remain substantially free of Plasmopara viticola (20 to 0% attack).

Example 3.13 Immunising action against Pseudomonas tomato on tomatoplants

A) Foliar application

After a cultivation period of 3 weeks, tomato plants are treated byfoliar application with a spray mixture (concentration: 0.02% activeingredient) prepared from a wettable powder formulation of the testcompound. After 2-3 days the plants are inoculated with a bacteriasuspension (10⁸ bacteria/ml) and incubated for 6 days at high humidityand at a temperature of 25° C. Evaluation of the protective action ismade 7-8 days after inoculation and is based on the bacteria attack.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 8 result in good immunisation againstPseudomonas tomato. Thus, plants treated e.g. with compound 1.16, 1.95or 7.5 remain substantially free of Pseudomonas (20 to 0% attack).

B) Soil application

After a cultivation period of 3 weeks, tomato plants are treated by soilapplication with a spray mixture (concentration: 0.002% activeingredient, based on the volume of the soil) prepared from a wettablepowder formulation of the test compound. After 2-3 days the plants areinoculated with a bacteria suspension (10⁸ bacteria/ml) and incubatedfor 6 days at high humidity and at a temperature of 25° C.

Evaluation of the protective action is made 7-8 days after inoculationand is based on the bacteria attack.

Untreated and infected control plants exhibit 100% attack in this test.

Compounds of Tables 1 to 7 result in good immunisation againstPseudomonas tomato. Thus, plants treated e.g. with compound 1.44, 1.95or 7.5 remain virtually completely free of Pseudomonas (20 to 0%attack).

Example 3.14 Immunising action against Phytophthora parasitica var.nicotianae on tobacco plants

Soil application

Tobacco plants (8 weeks old) are treated with a formulated solution ofthe test compound by soil application (concentration: 2 ppm, based onthe volume of the soil) or by injection into the leaf (concentration:0.02% active ingredient). After 4 days the plants are infected withPhytophthora parasitica. 2 ml of a zoospore suspension (8×10⁴ z/ml) arepipetted around the base of the stalk and washed into the soil withwater. The plants are kept at 24°-26° C. for 3 weeks.

Evaluation of the symptoms is made on the basis of the degree to whichthe plants have withered.

Untreated and infected plants had withered completely.

Compounds of Tables 1 to 7 exhibit good activity against Phytophthoraparasitica. Thus e.g. compound 1.2 reduces withering to 0-5%.

Example 3.15 Direct action against Phytophthora parasitica var.nicotianae

The test compound is mixed with nutrient substrate (V-8 agar) at aconcentration of 100 ppm and the mixture is poured into Petri dishes.After cooling, either a disc of mycelia (8 mm) is placed in the centreof the plate or 100 μl of a zoospore suspension (10⁵ spores/ml) of thefungus are spread onto the plate. The plates are incubated at 22° C.

Compound 1.2 exhibits no inhibiting activity on the germination andgrowth of the fungus in comparison with the control plates withoutactive ingredient.

Example 3.16 Immunising action against Peronospora tabacina on tobaccoplants

A) Foliar application

Tobacco plants (8 weeks old) are sprayed with a formulated solution ofthe test compound (concentration: 0.02% active ingredient). 4 days afterthe treatment the plants are inoculated with a sporangia suspension ofPeronospora tabacina (10⁴ sporangia/ml), kept in the dark for 20 hoursat 25° C. and high humidity, and then incubated further with normalday/night alternation.

B) Soil application

Tobacco plants (8 weeks old) are treated by soil application with aformulated solution of the test compound (concentration: 0.006% activeingredient, based on the volume of the soil). After 4 days the plantsare inoculated with a sporangia suspension of Peronospora tabacina (10⁴sporangia/ml), kept in the dark for 20 hours at 25° C. and highhumidity, and then incubated further with normal day/night alternation.

In tests A and B evaluation of the symptoms is made on the basis of thearea of the leaf surface attacked by the fungus.

The control plants exhibit 90 to 100% attack. Plants treated in tests Aand B with compound 1.2 exhibit 0-35% attack.

Example 3.17 Direct action against Peronospora tabacina

Formulated test compound is mixed at various concentrations (10, 1, 0.1ppm) with water agar and the mixture is poured into Petri dishes. Aftercooling, 100 μl of a sporangia suspension (10⁶ spores/ml) are spreadonto the plate. The plates are incubated at 18° C. for 16 hours.

In the case of e.g. compound 1.2, no inhibition of the germination ofPeronospora tabacina is observed.

Example 3.18 Immunising action against Cercospora nicotianae on tobaccoplants

A) Foliar application

Tobacco plants (8 weeks old) are sprayed with a formulated solution ofthe test compound (concentration: 200 ppm). Four days after thetreatment the plants are inoculated with a spore suspension ofCercospora nicotianae (10⁵ spores/ml) and incubated for 5 days at highhumidity and at a temperature of 22°-25° C. Incubation is then continuedat normal humidity and at 20°-22° C.

B) Soil application

Tobacco plants (8 weeks old) are treated by soil application with aformulated solution of the test compound (concentration: 0.002% activeingredient). After 4 days the plants are inoculated with a sporesuspension of Cercospora nicotianae (10⁵ spores/ml) and incubated for 5days at high humidity and at a temperature of 22°-25° C. Incubation isthen continued at normal humidity and at 20°-22° C.

In tests A and B evaluation of the symptoms is made on the basis of thefungus attack 12 to 14 days after infection.

The control plants exhibit 100% attack. Plants treated in tests A and Bwith compound 1.2 exhibit 0-20% attack.

Example 3.19 Direct action against Cercospora nicotianae

Test compound is mixed at various concentrations (100, 10, 1, 0.1 ppm)with nutrient substrate (V-8 agar) and the mixture is poured into Petridishes. After cooling, either a disc of mycelia (8 mm) is placed in thecentre of the plate or 100 μl of a spore suspension (5×10⁴ spores/ml)are spread onto the plate. The plates are incubated at 22° C.

Compound 1.2 exhibits no inhibiting activity on the germination andgrowth of the fungus in comparison with the control plates withoutactive ingredient.

Example 3.20 Immunising action against Pseudomonas tabaci on tobaccoplants

A) Foliar application

Tobacco plants (8 weeks old) are treated with a formulated solution ofthe test compound by spraying (concentration: 200 ppm) or by injection(concentration: 200, 60, 20 ppm). After 4 days the plants are sprayedwith a bacteria suspension (2×10⁷ bacteria/ml) and kept at high humidityand 22°-25° C. for 3 days. Incubation is then continued for 3 days atnormal humidity and 22°-25° C.

B) Soil application

Tobacco plants (8 weeks old) are treated by soil application with aformulated solution of the test compound (concentration: 0.002% to0.0002% active ingredient). After 4 days the plants are sprayed with abacteria suspension (2×10⁷ bacteria/ml) and kept at high humidity and22°-25° C. for 3 days. Incubation is then continued for 3 days at normalhumidity and 22°-25° C.

In test A and B evaluation of the symptous is made on the basis of thebacteria attack.

The control plants exhibit 100% attack.

Plants treated in tests A and B with compound 1.2 or 1.46 exhibit 0-20%attack.

Example 3.21 Direct action against Pseudomonas tabaci

The test compound is mixed at various concentrations (100, 10, 1, 0.1ppm) with liquid nutrient substrate (nutrient broth) containing 10⁶bacteria/ml, and the mixture is poured onto microtiter plates. Theplates are incubated at 22° C. and the growth of the bacteria isdetermined after 16 hours by measuring the optical density.

In the case of e.g. compound 1.2, no inhibition of the growth ofPseudomonas tabaci is observed. In contrast, streptomycin causes a 50%inhibition (EC₅₀) of growth at 0.1 ppm.

Example 3.22 Immunising action against tobacco mosaic virus and potatoY-virus on tobacco plants

Tobacco plants (8 weeks old) are treated with a formulated solution ofthe test compound by spraying (concentration: 200 ppm) or by injection(concentration: 0.02% to 0.0002% active ingredient). After 4 days theplants are inoculated by mechanical means with a suspension of tobaccomosaic virus (0.5 μg/ml+Carborundum) or of potato Y-virus (juice of aninfected leaf, 1 g/100 ml H₂ O+Carborundum) and incubated at atemperature of 20°-22° C.

Evaluation of the protective action is made in the case of tobaccomosaic virus on the basis of the number and size of local lesions 7 daysafter inoculation and in the case of potato Y-virus by serologicaldetermination of the number of viruses 7 and 10 days after inoculation.

In the test, plants treated with compound 1.2 exhibit, in the case oftobacco mosaic virus, 88 to 100% inhibition of the development oflesions in comparison with the corresponding controls (100% damage) and,in the case of potato Y-virus, 70 to 100% inhibition of the increase ofthe virus in comparison with the corresponding controls (=100%). Theuntreated and infected plants exhibit 100% lesions (control).

Example 3.23 Direct action against tobacco mosaic virus

The formulated test compound is added directly to the tobacco mosaicvirus inoculum (200 ppm+0.5 μg/ml virus+Carborundum). After one hour,tobacco plants (8 weeks old) are inoculated with the mixture bymechanical means.

Plants inoculated with this mixture of tobacco mosaic virus and compound1.2 exhibit no protective action.

Example 3.24 Immunising action against Erysiphe graminis on wheat

After a cultivation period of 5 days, wheat plants are sprayed with aspray mixture (concentration: 0.02%) prepared from a wettable powderformulation of the test compound. One day later the plants are infectedwith conidia of Erysiphe graminis and incubated at 20° C.

Evaluation of the protective action is made 8-10 days after infectionand is based on the fungus attack.

Compound of Tables 1 to 8 used as active ingredient exhibit goodactivity against Erysiphe graminis in this test. Thus, plants treatede.g. with compound 1.2 remain substantially free of Erysiphe attack (0to 20% damage). On the other hand, Erysiphe attack is 100% in untreatedand infected plants (control).

Example 3.25a In vitro test of direct action against Pyricularia oryzae,Colletotrichum lagenarium or Phytophthora infestans

The active ingredient of the test compounds is added a) to a liquid V-8medium (vegetable mixture) containing 10⁴ spores/ml of Pyriculariaoryzae or Colletotrichum lagenarium and b) to a liquid pea mediumcontaining 10⁴ sporangia/ml of Phytophthora infestans, the finalconcentration of active ingredient in both cases being 60 ppm. Theprepared nutrient media are placed on microtiter plates and kept therein the dark for 2 days at 22° C. and 100% relative humidity, thepreparation containing Pyricularia oryzae and Colletotrichum beingshaken.

The growth of the fungi is then determined by spectrometric absorptionmeasurement of the media at 595 nm (turbidity measurement).

Example 3.25b In vitro test of direct action against Xanthomonas oryzaeand Pseudomonas lachrymans

The active ingredient of the test compounds is added to a nutrientmedium (Bacto-Nutrient Broth Difco) containing 10⁶ organisms/ml ofXanthomonas oryzae or Pseudomonas lachrymans, the final concentration ofactive ingredient being 60 ppm. The prepared nutrient medium is placedon microtiter plates and shaken there the dark for 2 days at 22° C. and100% relative humidity.

The growth of the bacteria is then determined by spectrometricabsorption measurements of the media at 595 nm (turbidity measurement).

During testing of the active ingredient in the above-described tests,control experiments are carried out in parallel in the manner described,but without using active ingredients. The degree of turbidity measuredin the control experiments represents the 100% value for the evaluationscale used.

Evaluation is made on the basis of the following scale of ratings:Growth of fungus (in %) Rating

    ______________________________________                                        Growth of fungus (in %)                                                                          Rating                                                     ______________________________________                                        81-100              9*                                                        71-80               8*                                                        61-70               7*                                                        51-60              6                                                          41-50              5                                                          31-40              4                                                          21-30              3                                                          11-20              2                                                           0-10              1                                                          ______________________________________                                         *In the case of ratings greater than or equal to 7, it is concluded that      there is no direct microbicidal activity.                                

    __________________________________________________________________________    Fungicidal or bactericidal in vitro action of compounds of formula I in       comparison with known substances                                              __________________________________________________________________________    a) Test compounds of formula                                                   ##STR106##                                                                   Comp.              Colletotrichum                                                                        Pyricularia                                                                         Phytophthora                                                                         Xanthomonas                                                                          Pseudomonas                    no. Z              lagenarium                                                                            oryzae                                                                              infestans                                                                            oryzae lachrymans                     __________________________________________________________________________    1.  COOH           9       9     9      9      9                              1.2 COOMethyl      9       9     9      9      9                              1.4 COO-n-propyl   9       9     9      9      9                              1.135                                                                             COO-cyclohexyl 6       --    9      9      --                             1.34                                                                              COO-Benzyl     9       9     9      9      9                              1.96                                                                              COOCH.sub.2 -2'Furyl                                                                         --      9     4      --     9                              2.5 COS-Benzyl     9       9     9      9      9                              1.101                                                                             COOCH.sub.2 -2-Pyridinyl                                                                     9       9     6      9      9                              1.140                                                                             COOCH.sub.2 -2-Methylphenyl                                                                  9       9     9      9      9                              1.144                                                                             COOCH.sub.2 -3-Methoxyphenyl                                                                 9       --    9      9      --                             1.116                                                                             COOCH.sub.2 -1-Naphthyl                                                                      9       --    9      6      --                             1.108                                                                             COOCH.sub.2 CH.sub.2 P(O)(OMethyl).sub.2                                                     --      9     9      --     9                              1.104                                                                             COOCH.sub.2 CH.sub.2 Si(Methyl).sub.3                                                        --      3     9      --     9                              1.72                                                                               ##STR107##    --      9     9      --     9                              1.86                                                                              COO-Diaceton-D-glucosidyl                                                                    --      9     9      --     9                              3.1 CONH.sub.2     --      9     9      --     9                              3.26                                                                              CON(allyl).sub.2                                                                             --      9     9      --     8                              3.13                                                                               ##STR108##    --      6     9      --     9                              1.100                                                                              ##STR109##    9       9     --     9      --                             3.6 CONH-Phenyl    --      --    9      --     9                              3.9 CONHCH.sub.2 COOH                                                                            --      9     9      --     9                              7.26*                                                                             CN             --      9     9      --     8                              __________________________________________________________________________    b) Test compounds of formulae                                                 Verb.              Colletotrichum                                                                        Pyricularia                                                                         Phytophthora                                                                          Xanthomonas                                                                         Pseudomonas                    Nr. Formel         lagenarium                                                                            oryzae                                                                              infestans                                                                            oryzae lachrymans                     __________________________________________________________________________    7.6                                                                                ##STR110##    --      9     9      --     8                                   ##STR111##    1       1     1      --     --                             *                                                                                  ##STR112##    1       1     1      --     --                             __________________________________________________________________________     *Compounds from DEOS 1 695 786                                           

What is claimed is:
 1. A process for immunising plants against attack byphytopathogenic microorganisms which comprises applying as activeingredient to said plants and/or to the locus thereof a compound offormula I ##STR113## wherein: X is hydrogen, halogen, hydroxy, methyl,methoxy, HOOC or MOOC;Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro,hydroxy or amino, M being the molar equivalent of an alkali metal oralkaline earth metal ion that is formed from a corresponding base orbasic compound; and Z is cyano or --CO--A; A is UR, N(R₁)R₂ or U¹N(═C)_(n) (R₃)R₄ ; M is the molar equivalent of an alkali metal oralkaline earth metal ion that has been formed from a corresponding baseor basic compound; U is oxygen or sulfur; U¹ is oxygen or --N(R₅)--; Ris hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkyl that is substituted by halogen,cyano, nitro, hydroxy, U-C₁ -C₃ alkyl or by C₂ -C₄ dialkylamino or isinterrupted by the CO group, (T)--COOH or (T)--COOC₁ -C₄ alkyl, C₃ -C₆alkenyl, halo-substituted C₃ -C₆ alkenyl, C₃ -C₆ alkynyl,halo-substituted C₃ -C₆ alkynyl, (T)_(n) -C₃ -C₈ cycloalkyl, or a groupselected from the following: ##STR114## each of X^(a), X^(b) and X^(c),independently of the others, is hydrogen, halogen, hydroxy, cyano, HOOC,MOOC, C₁ -C₃ alkyl-OOC, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkylhaving up to 5 halogen atoms, or X^(a) is C₁ -C₂ haloalkoxy having up to5 halogen atoms, nitro, dimethylamino, phenyl, phenoxy, benzyloxy,sulfamoyl and X^(b) and X^(c) are both hydrogen; or X^(a) is phenyl,phenoxy or benzyloxy and X^(b) is halogen or methyl and X^(c) ishydrogen; or X^(a), X^(b) and X^(c) together are 4 or 5 fluorine atoms;naphth is a naphthyl radical that is unsubstituted or is substituted byhalogen, methyl, methoxy or by nitro; W is a 5- to 7-membered saturatedor unsaturated heterocycle having from 1 to 3 hetero atoms from thegroup O, N and S that is unsubstituted or is substituted by halogen,trifluoromethyl, cyano, C₁ -C₂ alkyl or by a C₁ -C₂ alkoxycarbonyl-C₂-C₄ alkyleneimino radical, or is a monosaccharide radical; T is a bridgemember --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)--, --CCH₃ (CH₃)--, --CH₂ CH₂CH₂ -- or --CH₂ CH₂ O--; R₁ is hydrogen, C₁ -C₅ alkyl, C₁ -C₅ alkylinterrupted by an oxygen or sulfur atom, C₁ -C₅ alkyl substituted byhalogen, cyano, HOOC or by C₁ -C₂ alkyl-OOC, C₁ -C₅ alkyl interrupted byan oxygen or sulfur atom and substituted by halogen, cyano, HOOC or byC₁ -C₂ alkyl-OOC, C₃ -C₅ alkenyl, C₃ -C₅ alkenyl substituted by C₁ -C₃alkyl-OOC, C₃ -C₅ alkynyl, C₃ -C₅ alkynyl substituted by C₁ -C₃alkyl-OOC, (T)_(n) -C₃ -C₆ cycloalkyl, (T)_(n) -C₃ -C₆ cycloalkylsubstituted by C₁ -C₃ alkyl-OOC, (T)_(n) -phenyl, or (T)_(n) -phenylsubstituted in the phenyl moiety by halogen, hydroxy, methyl, methoxy,CF₃, cyano, HOOC or by MOOC; R₂ is hydrogen, hydroxy, C₁ -C₃ alkyl, C₁-C₃ alkyl substituted by cyano or by C₁ -C₃ alkoxy, C₁ -C₄ alkoxy, a 3-to 6-membered saturated or unsaturated heterocycle containing O, N or Sas hetero atoms; R₁ and R₂ together are a heterocycle W; R₃ is hydrogen,cyano, C₁ -C₆ alkyl, phenyl, phenyl substituted by halogen, hydroxy,methyl, methoxy, HOOC or by MOOC, or a heterocycle W; R₄ is hydrogen, C₁-C₆ alkyl, CONH₂, CONH--CONH--C₁ -C₃ alkyl, C₁ -C₃ alkanoyl, C₁ -C₃alkanoyl substituted by halogen or by C₁ -C₃ alkoxy, C₃ -C₅ alkenoyl, orC₃ -C₅ alkenoyl substituted by halogen or by C₁ -C₃ alkoxy; R₃ and R₄together are a heterocycle W or a carbocyclic ring W'; W' is acarbocyclic radical having from 3 to 7 ring carbon atoms; R₅ is hydrogenor methyl; R₆ is hydrogen or C₁ -C₄ alkyl; and n is 0 or 1;and incompounds of formula I the organic radical A has a molecular weight ofless than 900; and in the case where U is oxygen or sulfur, also thesalts of the phytophysiologically tolerable 7-carboxylic acid withprimary, secondary or tertiary amines or with inorganic bases.
 2. Aprocess according to claim 1, wherein the application rate is less than1 kg of active ingredient/hectare.
 3. A process according to claim 1,which comprises applying a compound of formula I, wherein Z representscyano, X represents hydrogen, halogen or methyl and Y representshydrogen or halogen.
 4. A process according to claim 1, wherein1,2,3-benzothiadiazole-7-carboxylic acid or a salt thereof with a basiccompound is used as active ingredient.
 5. A process according to claim1, wherein 7-methoxycarbonylbenzo-1,2,3-thiadiazole is used as activeingredient.
 6. A process according to claim 1, wherein7-benzyloxycarbonylbenzo-1,2,3-thiadiazole is used as active ingredient.7. A process according to claim 1, wherein7-cyanobenzo-1,2,3-thiadiazole is used as active ingredient.
 8. Aprocess according to claim 1, wherein compounds of 7-C₂ -C₄alkoxycarbonylbenzo-1,2,3-thiadiazole are used as active ingredients. 9.A process for immunising plants against attack by phytopathogenicmicroorganisms which comprises applying as active ingredient to saidplants and/or to the locus thereof a compound of formula I' ##STR115##in which: X is hydrogen, halogen, hydroxy, methyl, methoxy, HOOC orMOOC;Y is hydrogen, halogen, SO₃ H, SO₃ M, nitro, hydroxy or amino; Z iscyano or COA; A is UR, N(R₁)R₂ or U¹ N(═C)_(n) (R₃)R₃)R₄ ; M is themolar equivalent of an alkali metal or alkaline earth metal ion that hasbeen formed from a corresponding base or basic compound; U is oxygen orsulfur; U¹ is oxygen or --N(R₅)--; R is hydrogen, C₁ -C₈ alkyl, C₁ -C₈alkyl substituted by halogen, cyano, nitro, hydroxy or by U-C₁ -C₃alkyl, (T)--COOH or (T)--COOC₁ -C₄ alkyl, C₃ -C₆ alkenyl,halo-substituted C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, halo-substituted C₃ -C₆alkynyl, (T)_(n) -C₃ -C₈ cycloalkyl, or a group selected from thefollowing: ##STR116## each of X^(a), X^(b) and X^(c), independently ofthe others, is hydrogen, halogen, hydroxy, cyano, HOOC, MOOC, C₁ -C₃alkyl-OOC, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkyl having up to 5halogen atoms; or X^(a) is C₁ -C₂ haloalkoxy having up to 5 halogenatoms, nitro, dimethylamino, phenyl, phenoxy, benzyloxy or sulfamoyloxyand X^(b) and X^(c) are both hydrogen; or X^(a) is phenyl, phenoxy orbenzyloxy and X^(b) is halogen or methyl and X^(c) is hydrogen; orX^(a), X^(b) and X^(c) together are 4 or 5 fluorine atoms; naphth is anaphthyl radical that is unsubstituted or is substituted by halogen,methyl, methoxy, or by nitro; W is a 5- to 7-membered saturated orunsaturated heterocycle having from 1 to 3 hetero atoms from the groupO, N and S that is unsubstituted or is substituted by halogen,trifluoromethyl, cyano, C₁ -C₂ alkyl or by a C₁ -C₂ alkoxycarbonyl-C₂-C₄ alkyleneimino radical, or is a monosaccharide radical; T is a bridgemember --CH₂ --, --CH₂ CH₂ --, --CH(CH₃)--, --CH₂ CH₂ CH₂ -- or --CH₂CH₂ O--; R₁ is hydrogen, C₁ -C₅ alkyl, C₁ -C₅ alkyl interrupted by anoxygen or sulfur atom, C₁ -C₅ alkyl substituted by halogen, cyano, HOOCor by C₁ -C₂ alkyl-OOC, C₁ -C₅ alkyl interrupted by an oxygen or sulfuratom and substituted by halogen, cyano, HOOC or by C₁ -C₂ alkyl-OOC, C₃-C₅ alkenyl, C₃ -C₅ alkenyl substituted by C₁ -C₃ alkyl-OOC, C₃ -C₅alkynyl, C₃ -C₅ alkynyl substituted by C₁ -C₃ alkyl-OOC, (T)_(n) -C₃ -C₆cycloalkyl, (T)_(n) -C₃ -C₆ cycloalkyl substituted by C₁ -C₃ alkyl-OOC,(T)_(n) -phenyl or (T)_(n) -phenyl substituted in the phenyl moiety byhalogen, hydroxy, methyl, CF₃, cyano, methoxy, HOOC or by MOOC; R₂ ishydrogen, hydroxy, C₁ -C₃ alkyl, C₁ -C₃ alkyl substituted by cyano or byC₁ -C₃ alkoxy, C₁ -C₄ alkoxy, or a 3- to 6-membered saturated orunsaturated heterocycle having O, N or S as hetero atoms; R₁ and R₂together are a heterocycle W; R₃ is hydrogen, cyano, C₁ -C₆ alkyl,phenyl, phenyl substituted by halogen, hydroxy, methyl, methoxy, HOOC orby MOOC, or a heterocycle W; R₄ is hydrogen, C₁ -C₆ alkyl, CONH₂,CONH--CONH-C₁ -C₃ alkyl, C₁ -C₆ alkanoyl, C₁ -C₃ alkanoyl substituted byhalogen or by C₁ -C₃ alkoxy, C₃ -C₅ alkenoyl, or C₃ -C₅ alkenoylsubstituted by halogen or by C₁ -C₃ alkoxy; R₃ and R₄ together are aheterocycle W or a carbocyclic ring W'; W' is a carbocyclic radicalhaving from 3 to 7 ring carbon atoms; R₅ is hydrogen or methyl; R₆ ishydrogen or C₁ -C₄ alkyl; and n is 0 or 1;with the exception of thecompounds: 7-cyanobenzo-1,2,3-thiadiazole;4-chloro-7-cyanobenzo-1,2,3-thiadiazole;4,6-dibromo-7-cyanobenzo-1,2,3-thiadiazole;benzo-1,2,3-thiadiazole-7-carboxylic acid;benzo-1,2,3-thiadiazole-7-carboxylic acid methyl ester.
 10. The processaccording to claim 9, with the proviso that if Z is cyano, HOOC ormethoxycarbonyl, each of X and Y, independently of the other, is nothydrogen, chlorine or bromine.
 11. The process according to claim 9,wherein the compounds of formula I' are selected from the groupconsisting of:7-n-pentoxycarbonylbenzo-1,2,3-thiadiazole;7-(4-methoxybenzyloxycarbonyl)-benzo-1,2,3-thiadiazole;7-(cycloheximino-oxycarbonyl)-benzo-1,2,3-thiadiazole;7-(3-hydroxy-n-propoxycarbonyl)-benzo-1,2,3-thiadiazole;1,2,5,6-di-O-isopropylidene-3-(7-benzo-1,2,3-thiadiazoyl)-D-glucofuranose;7-furfuryloxycarbonylbenzo-1,2,3-thiadiazole;7-(1,2,4-triazol-1-yl)-methoxycarbonylbenzo-1,2,3-thiadiazole;7-(2-pyridylmethoxycarbonyl)-benzo-1,2,3-thiadiazole;7-trimethylsilylmethoxycarbonylbenzo-1,2,3-thiadiazole;7-[2-(trimethylsilyl)-ethoxycarbonyl]-benzo-1,2,3-thiadiazole;7-dimethylphosphono-ethoxycarbonylbenzo-1,2,3-thiadiazole;7-cyclohexyloxycarbonylbenzo-1,2,3-thiadiazole;7-(1-phenethyloxycarbonyl)-benzo-1,2,3-thiadiazole;7-(3-methoxybenzyl)-benzo-1,2,3-thiadiazole;7-(ethylthiocarbonyl)-benzo-1,2,3-thiadiazole;7-(n-propylthiocarbonyl)-benzo-1,2,3-thiadiazole;7-(benzylthiocarbonyl)-benzo-1,2,3-thiadiazole;7-carbamoylbenzo-1,2,3-thiadiazole;7-N-phenylcarbamoylbenzo-1,2,3-thiadiazole;N-(7-benzo-1,2,3-thiadiazoyl)-glycine;7-(N-diallylcarbamoyl)-benzo-1,2,3-thiadiazole;6-fluoro-7-methoxycarbonylbenzo-1,2,3-thiadiazole;6-fluoro-7-carboxybenzo-1,2,3-thiadiazole;5-fluoro-7-benzyloxycarbonylbenzo-1,2,3-thiadiazole;5-fluoro-7-carboxybenzo-1,2,3-thiadiazole; and5-fluoro-7-ethoxycarbonylbenzo-1,2,3-thiadiazole.
 12. The processaccording to claim 9, wherein the compounds of formula I' are selectedfrom the group consisting of:7-ethoxycarbonylbenzo-1,2,3-thiadiazole;7-n-propoxycarbonylbenzo-1,2,3-thiadiazole;7-isopropoxycarbonylbenzo-1,2,3-thiadiazole;7-n-butoxycarbonylbenzo-1,2,3-thiadiazole;7-sec.-butoxycarbonylbenzo-1,2,3-thiadiazole;7-tert.-butoxycarbonylbenzo-1,2,3-thiadiazole;7-cyclopropylmethoxycarbonylbenzo-1,2,3-thiadiazole;7-(2'-phenethoxycarbonyl)-benzo-1,2,3-thiadiazole;7-benzyloxycarbonylbenzo-1,2,3-thiadiazole;7-allyloxycarbonylbenzo-1,2,3-thiadiazole;7-propyn-2-yloxycarbonylbenzo-1,2,3-thiadiazole;N-ethylaminocarbonyl-2-cyano-2-oximinocarbonylbenzo-1,2,3-thiadiazol-7-ylacetamide;sodium salt of benzo-1,2,3-thiadiazole-7-carboxylic acid; potassium saltof benzo-1,2,3-thiadiazole-7-carboxylic acid; triethylammonium salt ofbenzo-1,2,3-thiadiazole-7-carboxylic acid;7-(1'-phenethoxycarbonyl)-benzo-1,2,3-thiadiazole;7-(1'-naphthylmethoxycarbonyl)-benzo-1,2,3-thiadiazole;7-(methylthiocarbonyl)-benzo-1,2,3-thiadiazole;7-(ethylthiocarbonyl)-benzo-1,2,3-thiadiazole;7-(benzylthiocarbonyl)-benzo-1,2,3-thiadiazole;7-[(dicyanomethyl)-aminocarbonyl]-benzo-1,2,3-thiadiazole;1-amino-N-[(1,3,4-thiadiazol-2-yl)-(N-benzo-1,2,3-thiadiazoyl)]-2-methoxycarbonyl-1-propene;1-amino-N-[(1,3,4-thiadiazol-2-yl)-(N-benzo-1,2,3-thiadiazolyl)]-2-methoxycarbonyl-1-butene;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(methylpropylidene)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclobutylidene)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclopentylidene)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclohexylidene)-hydrazine;2-(benzo-1,2,3-thiadiazole-7-carbonyl)-1-(2'-sec.-butyl)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclopentyl)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cyclohexyl)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-(cycloheptyl)-hydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-1,2-diacetylhydrazine;1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-phenylhydrazine; and1-(benzo-1,2,3-thiadiazole-7-carbonyl)-2-pyridin-2'-ylhydrazine.
 13. Theprocess according to claim 12, wherein the compound is7-(methylthiocarbonyl)-benzo-1,2,3-thiadiazole.
 14. A composition forthe immunisation of plants against attack by phytopathogenicmicroorganisms, containing as active ingredient at least one compound ofthe formula I' defined in claim
 9. 15. A composition for theimmunisation of plants against attack by phytopathogenic microorganisms,containing as active ingredient at least one compound of the formula I'defined in claim
 10. 16. A composition for the immunisation of plantsagainst attack by phytopathogenic microorganisms, containing as activeingredient at least one compound of the formula I' defined in claim 11.17. A composition for the immunisation of plants against attack byphytopathogenic microorganisms, containing as active ingredient at leastone compound of the formula I' defined in claim
 12. 18. The compositionaccording to claim 14 wherein the active ingredient includes7-(methylthiocarbonyl)-benzo-1,2,3-thiadiazole.